Continuous process for the conversion of olefins and carbon dioxide to acrylates via solution phase reactor

ABSTRACT

Disclosed is a continuous process for producing α,β-unsaturated carboxylic acids or salts thereof, comprising: 1) in a first stage, contacting (a) a transition metal precursor compound comprising at least one first ligand, (b) optionally, at least one second ligand, (c) an olefin, (d) carbon dioxide (CO2), and (e) a diluent to form a first composition; 2) in a second stage, contacting a polyanionic solid with the first composition to form a second composition; and 3) in a third stage, (a) contacting the second composition with a polar solvent to release a metal salt of an α,β-unsaturated carboxylic acid and form a reacted solid. Methods of regenerating the polyanionic solid are described.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.16/001,171, filed Jun. 6, 2018, which claims the benefit of priority ofU.S. Provisional Patent Application No. 62/519,541, filed Jun. 14, 2017,both of which are incorporated herein by reference in their entireties.

TECHNICAL FIELD

This disclosure relates to routes of synthesis of acrylic acid and otherα,β-unsaturated carboxylic acids, including catalytic methods.

BACKGROUND

The majority of industrially synthesized chemical compounds are preparedfrom a limited set of precursors, whose ultimate sources are primarilyfossil fuels. As these reserves diminish, it would be beneficial to usea renewable resource, such as carbon dioxide, which is a non-toxic,abundant, and economical C₁ synthetic unit. The coupling of carbondioxide with other unsaturated molecules holds tremendous promise forthe direct preparation of molecules currently prepared by traditionalmethods not involving CO₂.

One could envision the direct preparation of acrylates and carboxylicacids through this method, when carbon dioxide is coupled with olefins.Currently, acrylic acid is produced by a two-stage oxidation ofpropylene. The production of acrylic acid directly from carbon dioxideand ethylene would represent a significant improvement due to thegreater availability of ethylene and carbon dioxide versus propylene,the use of a renewable material (CO₂) in the synthesis, and thereplacement of the two-step oxygenation process currently beingpracticed.

Therefore, what is needed are improved methods for preparing acrylicacid and other α,β-unsaturated carboxylic acids, including catalyticmethods.

SUMMARY OF THE DISCLOSURE

This summary is provided to introduce various concepts in a simplifiedform that are further described below in the detailed description. Thissummary is not intended to identify required or essential features ofthe claimed subject matter nor is the summary intended to limit thescope of the claimed subject matter.

In an aspect, this disclosure provides processes, including catalyticprocesses, for producing α,β-unsaturated carboxylic acids or saltsthereof utilizing a soluble or an insoluble polyanionic solid (anionicpolyelectrolyte) system. In particular, disclosed herein is a continuousprocess for producing an α,β-unsaturated carboxylic acid or saltthereof. When the polyanionic solid system is insoluble or the reactionsystem is otherwise heterogeneous, these processes represent animprovement over homogeneous processes that result in poor yields andinvolve challenging separation/isolation procedures. Moreover, theinsoluble polyanionic solid system is advantageous for the developmentof a continuous process. Therefore, conventional methods generally makeisolation of the desired α,β-unsaturated carboxylic acid (e.g., acrylicacid) difficult. In contrast, the processes disclosed herein utilize anpolyanionic solid comprising associated metal cations that generallyprovides a heterogeneous reaction mixture. When combined with a catalystsuch as a nickel catalyst, ethylene and carbon dioxide can be coupled toform a metalalactone, and the polyanionic solid can subsequentlydestabilize the metalalactone which eliminates a metal acrylate. Bydeveloping the disclosed heterogeneous system, there is now provided adistinct advantage in ease of separation of the desired product from thecatalytic system. Moreover, the polyanionic solid can result insurprisingly high yields of the desired α,β-unsaturated carboxylic acid,such as acrylic acid.

According to an aspect, one continuous process for producing anα,β-unsaturated carboxylic acid, or a salt thereof, can comprise:

-   -   1) in a first stage, contacting (a) a transition metal precursor        compound comprising at least one first ligand, (b) optionally,        at least one second ligand, (c) an olefin, (d) carbon dioxide        (CO₂), and (e) a diluent to form a first composition; and    -   2) in a second stage, contacting a polyanionic solid with the        first composition to form a second composition; and    -   3) in a third stage, (a) contacting the second composition with        a polar solvent to release a metal salt of an α,β-unsaturated        carboxylic acid and form a reacted solid; and (b) contacting the        reacted solid with a metal-containing base to produce a        regenerated polyanionic solid.

In a further aspect, there is provided another such continuous processfor producing an α,β-unsaturated carboxylic acid or salt thereof, andthis process can comprise:

-   -   1) in a first stage, contacting (a) a transition metal precursor        compound comprising at least one first ligand, (b) optionally,        at least one second ligand, (c) an olefin, (d) carbon dioxide        (CO₂), and (e) a diluent to form a first composition comprising        a metalalactone compound; and    -   2) in a second stage, contacting a polyanionic solid with the        first composition to form a second composition; and    -   3) in a third stage, (a) contacting the second composition with        polar solvent to release a metal salt of an α,β-unsaturated        carboxylic acid and form a reacted solid; and (b) contacting the        reacted solid with a metal-containing base to produce a        regenerated polyanionic solid.        In this aspect, for example, the first composition includes a        metalalactone compound that is formed from the recited reactants        and, in addition to the metalalactone portion of the molecule,        the metalalactone compound can include at least one additional        ligand, which can be at least one first ligand and/or at least        one second ligand. For example, a transition metal precursor        compound can be Ni(COD)₂, and one suitable second ligand can be        a diphosphine ligand, and the metalalactone compound can        comprise the nickelalactone moiety and the diphosphine ligand.

According to this and other aspects of the disclosure, the metalalactonecompound may also be described as a metalalactone comprising at leastone ligand or simply a metalalactone, and these terms are usedinterchangeably to reflect that the metalalactone compound comprises atleast one ligand in addition to the metalalactone moiety. Similarly,reference to a metalalactone ligand refers to any ligand of themetalalactone compound other than the metalalactone moiety.

The polyanionic solid and any associated cations such as associatedmetal cations are described in detail herein.

According to additional aspects of this disclosure, there is provided acontinuous process for producing an α,β-unsaturated carboxylic acid orsalt thereof, in which the process can comprise:

-   -   1) in a first stage, obtaining or providing a first composition        comprising a metalalactone compound and a diluent;    -   2) in a second stage, contacting a polyanionic solid with the        first composition to form a second composition; and    -   3) in a third stage, (a) contacting the second composition with        a polar solvent to release a metal salt of an α,β-unsaturated        carboxylic acid and form a reacted solid; and (b) contacting the        reacted solid with a metal-containing base to produce a        regenerated polyanionic solid.        In an aspect, in the second stage of this continuous process for        producing an α,β-unsaturated carboxylic acid or salt thereof,        the second composition can comprise an adduct of the        metalalactone and the polyanionic solid.

In a further aspect, there is provided a continuous process forproducing an α,β-unsaturated carboxylic acid or salt thereof, theprocess comprising:

-   -   1) in a first stage, contacting (a) a Group 8-10 transition        metal precursor compound comprising at least one first        ligand, (b) optionally, at least one second ligand, (c) an        olefin, (d) carbon dioxide (CO₂), and (e) a diluent to form a        first composition comprising a metalalactone compound; and    -   2) in a second stage, contacting an anionic polyaromatic resin        comprising associated metal cations with the first composition        to form a second composition comprising an adduct of the        metalalactone compound and the anionic polyaromatic resin; and    -   3) in a third stage, (a) contacting the second composition with        water to release a metal salt of an α,β-unsaturated carboxylic        acid and form a reacted polyaromatic resin; and (b) contacting        the reacted polyaromatic resin with a metal-containing base to        produce a regenerated polyanionic solid.

This summary and the following detailed description provide examples andare explanatory only of the invention. Accordingly, the foregoingsummary and the following detailed description should not be consideredto be restrictive. Additional features or variations thereof can beprovided in addition to those set forth herein, such as for example,various feature combinations and sub-combinations of these described inthe detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1. illustrates an aspect of this disclosure, showing the use anpolyanionic solid stationary phase in a column configuration, in whichformation of the acrylate coupling reaction of ethylene and CO₂ to forma metalalactone such as a nickelalactone in a mobile phase can beeffected, and the resulting nickelalactone destabilized by thepolyelectrolyte stationary phase to form an acrylate product.

FIG. 2. illustrates certain conceptual aspects of the process, showingthe concept for a continuous process for producing an α,β-unsaturatedcarboxylic acid or salt thereof based upon the reaction process ofFIG. 1. For example, FIG. 2 illustrates 1) a first stage in which anickel precursor compound comprising at least one first ligand (Ln-Ni),optionally, at least one second ligand (also generically represented asLn), ethylene, carbon dioxide (CO₂), and toluene (a diluent) arecombined to form a first composition which includes a nickelalactone; 2)a second absorption/elimination stage, in which a polyanionic solid(also termed cocatalyst or activator) is contacted with the firstcomposition to form a second composition, which can include an adduct ofthe nickelalactone and the polyanionic solid; and 3) a third stage inwhich (a) the second composition (typically comprising thenickelalactone-polyanionic solid adduct) is contacted with a polarsolvent to release a metal salt of an α,β-unsaturated carboxylic acidand form a reacted solid, and (b) reacted solid (cocatalyst) iscontacted with a metal-containing base to produce a regeneratedpolyanionic solid. FIG. 2 also illustrates an optional fourth stage inwhich the regenerated polyanionic solid is dried or partially dried. Thedashed lines between the second stage, third stage and optional fourthstage are to illustrate that the vessels alternate between the stages.

DETAILED DESCRIPTION OF THE DISCLOSURE Definitions

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2^(nd) Ed (1997) can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

While compositions and methods are described in terms of “comprising”various components or steps, the compositions and methods can also“consist essentially of” or “consist of” the various components orsteps, unless stated otherwise.

The terms “a,” “an,” and “the” are intended to include pluralalternatives, e.g., at least one. For instance, the disclosure of “apolyanionic solid,” “a diluent,” “a catalyst,” and the like, is meant toencompass one, or mixtures or combinations of more than one, polyanionicsolid, diluent, catalyst, and the like, unless otherwise specified.

The terms “including”, “with”, and “having”, as used herein, are definedas comprising (i.e., open language), unless specified otherwise.

The term “hydrocarbon” refers to a compound containing only carbon andhydrogen. Other identifiers can be utilized to indicate the presence ofparticular groups in the hydrocarbon, for instance, a halogenatedhydrocarbon indicates the presence of one or more halogen atomsreplacing an equivalent number of hydrogen atoms in the hydrocarbon.

As used herein, the term “α,β-unsaturated carboxylic acid” and itsderivatives refer to a carboxylic acid having a carbon atom of acarbon-carbon double bond attached to the carbonyl carbon atom (thecarbon atom bearing the double bonded oxygen atom). Optionally, theα,β-unsaturated carboxylic acid can contain other functional groups,heteroatoms, or combinations thereof.

The term “polyanionic” is used interchangeably with “anionicpolyelectrolyte” and is used to mean a polymeric (macromolecular),organic or inorganic, extended substance which comprises amultiply-charged polyion, together with an equivalent amount of counterions. Therefore, a “polyanionic solid” or “anionic polyelectrolyte”refers to a material that comprises a multiply-charged polyanion,together with an equivalent amount of cations. The charge on the polyiontypically resides on heteroatoms such as oxygen, nitrogen or sulfur, oron groups such as sulfonate. The structural part of the polyelectrolytethat bears the charged moieties can be pendant groups off a polymerbackbone or can be part of the polymeric backbone itself. The term“polyelectrolyte” or “polyanionic” material may be used to refer to bothsoluble species and insoluble species, such as some of thepoly(vinylphenol)-based materials, the phenol-formaldehyde basedmaterials described herein, or the chemically-treated solid oxidematerials described herein. The multiply-charged polyanion may also bereferred to as a base, and the associated metal ion as simply a counterion, metal ion, or Lewis acid as appropriate.

Although the terms “polyphenol” and “polyaromatic” are used herein todescribe polyanionic materials in which a phenoxide moiety carries thenegative charge in the polyelectrolyte, and although these terms may beused interchangeably as the context allows, these terms are generallyused herein to describe specific types of polyanionic materials oranionic polyelectrolyte polymers, that are somewhat different, as setout here.

[1] The terms “polyphenol” and “polyphenoxide” are generally used hereinto describe a specific type of anionic polyelectrolyte polymer, forexample, the polymeric materials such as poly(4-vinylphenol) andmetallated poly(4-vinylphenoxide) that typically include a pendantphenol, phenoxide, or substituted analogs thereof that are bonded to apolymeric backbone. Therefore, the oxygen of the phenoxide group bearsthe negative charge.

[2] The term “polyaromatic” is also generally used herein to describe aspecific type of anionic polyelectrolyte resin or polymer, for example,the phenol-formaldehyde crosslinked resins and their analogs, in whichthe phenol aromatic group and methylene moieties are part of an extendedcrosslinked network. Therefore, aromatic groups in the “polyaromatic”structure are hydroxylated, hydroxymetallated, or otherwisefunctionalized with a group that carries the negative charge in theanionic polyelectrolyte (e.g. thiolate, alkyl amide). Crosslinkednetworks that are prepared using various phenol or polyhydroxyareneco-monomers also included in this definition. The term “phenolic resin”may be used to describe these materials as well.

A “polyhydroxyarene” is used herein to a phenol-type monomer thatincludes more than one hydroxyl group. Resorcinol (also termed,benzenediol or m-dihydroxybenzene) is a typical polyhydroxyarene.

The terms “chemically-treated solid oxide,” “treated solid oxide,” andthe like, are used herein to indicate a solid, inorganic oxide ofrelatively high porosity, which can exhibit Lewis acidic or Brønstedacidic behavior, and which has been treated with an electron-withdrawingcomponent, typically an anion, and generally which has been calcined.The electron-withdrawing component is typically an electron-withdrawinganion source compound. Thus, the chemically-treated solid oxide cancomprise a calcined contact product of at least one solid oxide with atleast one electron-withdrawing anion source compound. Typically, thechemically-treated solid oxide comprises at least one acidic solid oxidecompound. The terms “activator”, “activator-support”, and “co-catalyst”are also used herein to describe the solid oxide chemically-treated withan electron withdrawing anion, or “chemically-treated solid oxide”, andthese terms may be used interchangeably, regardless of any actualactivating mechanism.

For any particular compound or group disclosed herein, any name orstructure presented is intended to encompass all conformational isomers,regioisomers, stereoisomers, and mixtures thereof that can arise from aparticular set of substituents, unless otherwise specified. The name orstructure also encompasses all enantiomers, diastereomers, and otheroptical isomers (if there are any) whether in enantiomeric or racemicforms, as well as mixtures of stereoisomers, as would be recognized by askilled artisan, unless otherwise specified. For example, a generalreference to pentane includes n-pentane, 2-methyl-butane, and2,2-dimethylpropane; and a general reference to a butyl group includes an-butyl group, a sec-butyl group, an iso-butyl group, and a t-butylgroup.

Various numerical ranges are disclosed herein. When Applicants discloseor claim a range of any type, Applicants' intent is to disclose or claimindividually each possible number that such a range could reasonablyencompass, including end points of the range as well as any sub-rangesand combinations of sub-ranges encompassed therein, unless otherwisespecified.

For example, by disclosing a temperature of from 70° C. to 80° C.,Applicant's intent is to recite individually 70° C., 71° C., 72° C., 73°C., 74° C., 75° C., 76° C., 77° C., 78° C., 79° C., and 80° C.,including any sub-ranges and combinations of sub-ranges encompassedtherein, and these methods of describing such ranges areinterchangeable. Moreover, all numerical end points of ranges disclosedherein are approximate, unless excluded by proviso. As a representativeexample, if Applicants disclose in an aspect of the disclosure that oneor more steps in the processes disclosed herein can be conducted at atemperature in a range from 10° C. to 75° C., this range should beinterpreted as encompassing temperatures in a range from “about” 10° C.to “about” 75° C.

Values or ranges may be expressed herein as “about”, from “about” oneparticular value, and/or to “about” another particular value. When suchvalues or ranges are expressed, other embodiments disclosed include thespecific value recited, from the one particular value, and/or to theother particular value. Similarly, when values are expressed asapproximations, by use of the antecedent “about,” it will be understoodthat the particular value forms another embodiment. It will be furtherunderstood that there are a number of values disclosed therein, and thateach value is also herein disclosed as “about” that particular value inaddition to the value itself. In another aspect, use of the term “about”means ±20% of the stated value, ±15% of the stated value, ±10% of thestated value, ±5% of the stated value, or ±3% of the stated value.

Applicants reserve the right to proviso out or exclude any individualmembers of any such group of values or ranges, including any sub-rangesor combinations of sub-ranges within the group, that can be claimedaccording to a range or in any similar manner, if for any reasonApplicants choose to claim less than the full measure of the disclosure,for example, to account for a reference that Applicants can be unawareof at the time of the filing of the application. Further, Applicantsreserve the right to proviso out or exclude any individual substituents,analogs, compounds, ligands, structures, or groups thereof, or anymembers of a claimed group, if for any reason Applicants choose to claimless than the full measure of the disclosure, for example, to accountfor a reference that Applicants can be unaware of at the time of thefiling of the application.

The term “substituted” when used to describe a group, for example, whenreferring to a substituted analog of a particular group, is intended todescribe the compound or group wherein any non-hydrogen moiety formallyreplaces hydrogen in that group or compound, and is intended to benon-limiting. A compound or group can also be referred to herein as“unsubstituted” or by equivalent terms such as “non-substituted,” whichrefers to the original group or compound. “Substituted” is intended tobe non-limiting and include inorganic substituents or organicsubstituents as specified and as understood by one of ordinary skill inthe art.

The terms “contact product,” “contacting,” and the like, are used hereinto describe compositions and methods wherein the components arecontacted together in any order, in any manner, and for any length oftime, unless specified otherwise. For example, the components can becontacted by blending or mixing. Further, unless otherwise specified,the contacting of any component can occur in the presence or absence ofany other component of the compositions and methods described herein.Combining additional materials or components can be done by any suitablemethod. Further, the term “contact product” includes mixtures, blends,solutions, slurries, reaction products, and the like, or combinationsthereof. Although “contact product” can, and often does, includereaction products, it is not required for the respective components toreact with one another. Similarly, “contacting” two or more componentscan result in a reaction product or a reaction mixture. Consequently,depending upon the circumstances, a “contact product” can be a mixture,a reaction mixture, or a reaction product.

Although any methods and materials similar or equivalent to thosedescribed herein can be used in the practice or testing of theinvention, the typical methods and materials are herein described.

All publications and patents mentioned herein are incorporated herein byreference for the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention. The publications discussed throughout the text are providedsolely for their disclosure prior to the filing date of the presentapplication. Nothing herein is to be construed as an admission that theinventors are not entitled to antedate such disclosure by virtue ofprior invention.

The present disclosure is directed generally to methods for formingα,β-unsaturated carboxylic acids, or salts thereof. An illustrativeexample of a suitable α,β-unsaturated carboxylic acid is acrylic acid.

Formation of α,β-Unsaturated Carboxylic Acids and Salts

According to one aspect, this disclosure provides for the formation ofan α,β-unsaturated carboxylic acids and salts thereof frommetalalactones and polyanionic solids. One example of theα,β-unsaturated carboxylic acid salt formation from exemplarymetalalactones and polyanionic solids is illustrated in Scheme 1, whichprovides for a nickel catalytic coupling reaction between an olefin andCO₂ and formation of an acrylate. As explained herein, Scheme 1 is notlimiting but is exemplary, and each reactant, catalyst, polymer, andproduct are provided for illustrative purposes.

In Scheme 1, a transition metal catalyst as disclosed herein isillustrated generally by a nickel(0) catalyst at compound 1, and theolefin disclosed herein, generally an α-olefin, is illustrated generallyby ethylene. In the presence of the catalyst 1, the olefin couples withCO₂ to form the metalalactone 2. Metalalactone 2 is destabilized by itsinteraction with an polyanionic solid, an example of which is shown inScheme 1 as a metal poly(4-vinylphenoxide) 3. While not intending to bebound by theory, metal poly(4-vinylphenoxide) 3 is thought to interactwith metalalactone 2 in some way, for example to form an adduct of sometype, such as one illustrated as intermediate 4. Reaction with thecombined metal poly(4-vinylphenoxide) 3 and metalalactone 2 (orintermediate of some type, represented generally as 4) then proceeds toeliminate or release the metal acrylate 6, for example, fromintermediate 4, and regenerates catalyst compound 1 and byproductneutral polymer 5 (here, poly(4-vinylphenol), which is regenerated tothe polyanionic solid reactant, for example metal poly(4-vinylphenoxide)3, upon its reaction with the base 7. The participation of the polarsolvent and/or base in the elimination or release of the metal acrylate6, is not fully understood at this time and may include directparticipation in the mechanism or simply solvating an acrylate saltwhich is insoluble in the diluent. In other words, elimination of themetal acrylate from 4 occurs to regenerate catalyst compound 1 andbyproduct neutral polymer 5 (here, poly(4-vinylphenol)), which isregenerated to the polyanionic solid reactant 3 upon its reaction with abase 7. In the presence of additional ethylene and CO₂, catalyst 1 isconverted to metalalactone 2.

One exemplary base illustrated in Scheme 1 is a hydroxide base, but acarbonate base, similar inorganic bases, and a wide range of other basescan be used, particularly metal-containing bases. Metal containing basescan include any basic inorganic metal compound or mixture of compoundsthat contain metal cations or cation sources, for example, alkali andalkaline earth metal compounds such as oxides, hydroxides, alkoxides,aryloxides, amides, alkyl amides, arylamides, hydrides and carbonateslike calcium carbonate. In an aspect, the reaction of Scheme 1 can beconducted using certain bases as disclosed, but if desired, otherorganic bases such as some alkoxide, aryloxide, amide, alkyl amide,arylamide bases, or the like can be excluded. Typically, the inorganicbases such as alkali metal hydroxides have been found to work well.

Polyanionic Solids (Anionic Polyelectrolytes) and Associated Cations

Generally, the polyanionic solid comprising associated metal cationsused in the processes disclosed herein can comprise (or consistessentially of, or consist of) an insoluble polyanionic solid, a solubleanionic polyelectrolyte, or a combination thereof. That is, thepolyanionic solid material can be soluble, insoluble, or only partiallyor slightly soluble in the diluent or reaction mixture. It is furthercontemplated that mixtures or combinations of two or more polyanionicsolids can be employed in certain aspects of the disclosure. Therefore,the “polyanionic solid” is a polymeric or extended lattice solid,organic or inorganic material, which comprises a multiply-chargedpolyanion, together with an equivalent amount of counter cations, and isused generally to refer to both soluble materials and insolublematerials.

In an aspect, the polyanionic solid comprising associated cations can beused in the absence of an alkoxide or aryloxide base. Further, thereactions and processes disclosed herein can be conducted in the absenceof an alkoxide, an aryloxide, an alkylamide, an arylamide, and/orsubstituted analogs thereof. That is, additional bases with theirassociated counter ions are not required to effect the processesdisclosed herein.

According to an aspect, the polyanionic solid comprising associatedcations used in the processes can be used in the absence of a solidsupport. That is the polyanionic solid can be used is its naturalpolymeric form without being bonded to or supported on any insolublesupport, such as an inorganic oxide or mixed oxide material.

Alkoxylated Polymers and Related Polyanionic Solids

In an aspect, the term polyanionic solid (or anionic polyelectrolyte) isused to refer to and include such polyanionic solids that comprisealkoxide, aryloxide, acrylate, (meth)acrylate, sulfonate, alkylthiolate, aryl thiolate, alkyl amide, or aryl amine groups, along withassociated metal cations, such as any alkali metal cation, alkalineearth cation, or metal cations having varying Lewis acidities. Whileaspects of this disclosure are exemplified with polyanionic solidshaving aryloxide (or “phenoxide”) anionic groups, these are to beconsidered exemplary of any of the polyanionic solids provided herein.Therefore, terms such as poly(vinyl aryloxide), poly(vinyl phenoxide),poly(hydroxystyrene), and the like are generally used interchangeablyunless the context provides otherwise.

Accordingly, the term anionic polyelectrolyte or polyanionic solid isused generally to include such polyanionic solids as a poly(vinylaryloxide), a poly(vinyl alkoxide), a poly(acrylate), apoly((meth)acrylate)), a poly(styrene sulfonate), a phenol-formaldehyderesin, a polyhydroxyarene-formaldehyde resin (such as aresorcinol-formaldehyde resin), a polyhydroxyarene- andfluorophenol-formaldehyde resin (such as a resorcinol- and2-fluorophenol-formaldehyde resin), a poly(vinyl arylamide), apoly(vinyl alkylamide), or combinations thereof, along with associatedmetal cations. Polymers that generally fall under thephenol-formaldehyde type of crosslinked resins may be referred to aspolyaromatic resins. Co-polymers of these specific types of polyanionicsolids are also included in this disclosure. The polyelectrolyte corestructure can be substituted on the polymer backbone or the pendantgroups that also contain the typical oxygen, nitrogen, or sulfurheteroatoms, and such substituted variations are included in thisdisclosure and use of the term polyanionic solid. For example, any ofthe polyanionic solids can be substituted with electron-withdrawinggroups or electron-donating groups or even combinations thereof.

Anionic polyelectrolytes (polyanionic solids) such as those used hereininclude associated cations, particularly associated metal cations,including Lewis acidic metal cations and cations with low Lewis acidity.According to an aspect, the associated metal cations can be an alkalimetal, an alkaline earth metal, or any combination thereof. Typicalassociated metal cations can be, can comprise, or can be selected fromlithium, sodium, potassium, magnesium, calcium, strontium, barium,aluminum, or zinc, and the like. Generally, sodium or potassiumassociated metal cations have been found to work well. Therefore,cations with a range of Lewis acidities in the particular solvent can beuseful according to this disclosure.

One aspect of the disclosed process provides for using an polyanionicsolid that comprises, consists essentially of, or consists ofsodium(polyvinylphenoxide), including sodium(poly-4-vinylphenoxide).Other salts, such as the potassium salt, of the poly-4-vinylphenoxideare also useful.

In a further aspect, useful polyanionic solids can includephenol-formaldehyde resins, which are cross-linked materials derivedfrom the condensation reaction of phenol with formaldehyde, that aretreated with a base or a metal cation source. Advantages of usingtreated phenol-formaldehyde resins include their insolubility, whichallows the use of a range of solvents with these materials, and theirrelatively high phenol concentration that can be functionalized using ametal base such as an alkali metal hydroxide. An early version of thethermosetting phenol formaldehyde resins formed from the condensationreaction of phenol with formaldehyde is Bakelite®, and variousphenol-formaldehyde resins used herein may be referred to generically as“Bakelite” resins. In the context of this disclosure, the use of termssuch as Bakelite or general terms such as phenol-formaldehyde resinscontemplates that these materials will be treated with ametal-containing base or a metal cation source such as sodium hydroxideprior to their use in the processes disclosed.

In addition, other useful polyanionic solids include substitutedphenol-formaldehyde resins that are also generally crosslinked intoinsoluble resins. These resins can be formed from the condensationreaction of one or more of phenol, a polyhydroxyarene such as resorcinol(also, benzenediol or m-dihydroxybenzene), and/or their substitutedanalogs with formaldehyde. Therefore, these materials include resinsmade with more than one phenol as co-monomer. Treatment with bases suchas NaOH or KOH also provides a ready method of functionalizing thepolyaromatic polymers for the reactivity described herein.

In one example, a resin can be prepared using the monomer combination ofresorcinol (m-dihydroxybenzene) and fluorophenol monomers withformaldehyde, and sodium-treated to generate the polyanionic solid.While not intending to be theory bound, the meta-dihydroxybenzene isbelieved to add additional ion chelation functionality to the resin.Subsequent base (e.g. sodium hydroxide) treatment can be used togenerate the polyanionic solid.

Finally, this aspect is not intended to be limiting. Therefore, othersuitable polyanionic solids that can be used include a number ofpolyanionic solids which include carboxylic acid/carboxylate groups.Examples include but are not limited to polyacrylic acid,polymethacrylic acid, poly(D,L-glutamic) acid, polyuronic acid (alginic,galacturonic, glucuronic, and the like), glycosaminoglycans (hyaluronicacid dermatan sulphate, chondroitin sulphate, heparin, heparan sulphate,and keratan sulphate), poly(D,L-aspartic acid), poly(styrene sulfonate),poly(phosphate), polynucleic acids, and so forth.

In those aspects and embodiments in which polymer support variations areused and/or in which the polyelectrolyte itself is a solid that isinsoluble in the diluent of the reaction, such solid statepolyelectrolyte embodiments can have any suitable surface area, porevolume, and particle size, as would be recognized by those of skill inthe art. For instance, the solid polyelectrolyte can have a pore volumein a range from 0.1 to 2.5 mL/g, or alternatively, from 0.5 to 2.5 mL/g.In a further aspect, the solid polyelectrolyte can have a pore volumefrom 1 to 2.5 mL/g. Alternatively the pore volume can be from 0.1 to 1.0mL/g. Additionally, or alternatively, the solid polyelectrolyte can havea BET surface area in a range from 10 to 750 m²/g; alternatively, from100 to 750 m²/g; or alternatively, from 100 to 500 m²/g or alternativelyfrom 30 to 200 m²/g. In a further aspect, the solid polyelectrolyte canhave a surface area of from 100 to 400 m²/g, from 200 to 450 m²/g, orfrom 150 to 350 m²/g. Surface area, pore diameter, and pore volume weremeasured by Brunauer, Emmett and Teller (BET) technique with nitrogengas used as the probe. The average particle size of the solidpolyelectrolyte can vary greatly depending upon the process specifics,however, average particle sizes in the range of from 5 to 500 μm, from10 to 250 μm, or from 25 to 200 μm, are often employed. Alternatively ⅛inch (3.2 mm) to ¼ inch (6.4 mm) pellets or beads can also be used. Inan aspect, the average or median particle size is measured by eitherdynamic light scattering tests or by a laser diffraction technique.

The present disclosure also provides for various modifications of thepolymeric anionic stationary phase (polyanionic solids), for example, ina column or other suitable solid state configuration. Further variousmodifications of the polymeric anionic stationary phase (polyanionicsolids), for example, in a column or other suitable solid stateconfiguration are useful in the processes disclosed herein. For example,acid-base reactions that generate the polyanionic solid from the neutralpolymer can be effected using a wide range of metal bases, includingalkali and alkaline hydroxides, alkoxides, aryloxides, amides, alkyl oraryl amides, and the like, such that an assortment of electrophiles canbe used in nickelalactone destabilization as demonstrated herein for thepolyvinylphenols.

Polymer modifications can also include using variants of thepoly(vinylphenol), that can be prepared by polymerization of protectedhydroxyl-substituted styrenes (such as acetoxystyrene) having a varietyof organic and inorganic substituents, such as alkyls, halogens, andheteroatom substituents, typically followed by hydrolysis. Suchadjustments can provide flexibility for tailoring the reaction accordingto the specific olefin to be coupled with CO₂, the reaction rate, thecatalytic turnover, as well as additional reaction parameters andcombinations of reaction parameters.

In a further aspect, polymer modifications can also include usingco-polymers based on, for example, the co-polymerization of a protectedhydroxyl-substituted styrene with other monomers (e.g., styrenes and/or(meth)acrylates) to produce libraries of polymeric electrophiles. Such alibrary can be utilized to test and match the specific polyanionic solidwith the specific olefin, to improve or optimize reaction rate,catalytic turnover, reaction selectivity, and the like. Further polymersupport variations can also be used, for example, polymers can besupported onto beads or other surfaces. Alternatively, one class ofpolymer support variation that is possible for use with this technologyis the cast polymer that can function as an ion exchange membrane.Alternatively, the polyanionic solid can be unsupported and used in theabsence of any support.

Chemically-Treated Solid Oxide as Polyanionic Solids

In one aspect, this disclosure encompasses a continuous process asdescribed herein, in which the polyanionic solid (also termed anactivator or co-catalyst) can comprise a metal oxide. In an aspect, thepolyanionic solid can comprise a calcined metal oxide. Examples of metaloxides include, but are not limited to, silica, alumina, silica-alumina,silica-coated alumina, aluminum phosphate, aluminophosphate,heteropolytungstate, mullite, boehmite, titania, zirconia, magnesia,boria, zinc oxide, silica-titania, silica-zirconia, a mixed oxidethereof, or any mixture thereof. The polyanionic solid can comprise, forexample, metal-treated sodium oxide. The polyanionic solid can comprisea solid oxide that has been contacted with the metal-containing base,for example, the polyanionic solid can comprise a chemically-treatedsolid oxide that has been hydroxylated and subsequently contacted withthe metal-containing base.

In an aspect, the polyanionic solid can comprise, consist of, consistessentially or, or be selected from a chemically-treated solid oxide.The term “chemically-treated solid oxide” is used interchangeably withsimilar terms such as, “solid oxide treated with an electron-withdrawinganion,” “treated solid oxide,” While not intending to be bound bytheory, it is thought that the chemically-treated solid oxide can serveas an acidic activator-support which allows it to function as thepolyanionic solid in the continuous process disclosed herein.

In one aspect of this disclosure, the polyanionic solid can comprise atleast one chemically-treated solid oxide comprising at least one solidoxide treated with at least one electron-withdrawing anion, wherein thesolid oxide can comprise any oxide that is characterized by a highsurface area, and the electron-withdrawing anion can comprise any anionthat increases the acidity of the solid oxide as compared to the solidoxide that is not treated with at least one electron-withdrawing anion.

In another aspect of this disclosure, the polyanionic solid can compriseat least one chemically-treated solid oxide, comprising at least onesolid oxide treated with at least one electron-withdrawing anion. Forexample, the solid oxide can comprise or can be selected from at leastone of silica, alumina, silica-alumina, silica-coated alumina, aluminumphosphate, aluminophosphate, heteropolytungstate, mullite, boehmite,titania, zirconia, magnesia, boria, zinc oxide, silica-titania,silica-zirconia, a mixed oxide thereof, or any mixture thereof. Theseoxides can be chemically treated with at least one electron withdrawinganion to provide the polyanionic solid. For example, the at least oneelectron withdrawing anion can comprise or can be selected fromfluoride, chloride, bromide, iodide, phosphate, triflate,trifluoroacetate, sulfate, bisulfate, fluorosulfate, fluoroborate,fluorophosphate, fluorozirconate, fluorotitanate, phosphotungstate, orsimilar anions, or any combination thereof.

In an aspect, the continuous process according to this disclosure, thechemically-treated solid oxide comprises, consists of, consistsessentially of, or is selected from fluorided alumina, chloridedalumina, bromided alumina, fluorided-chlorided alumina, sulfatedalumina, fluorided silica-alumina, chlorided silica-alumina, bromidedsilica-alumina, fluorided-chlorided silica-alumina, sulfatedsilica-alumina, fluorided silica-titania, chlorided silica-titania,bromided silica-titania, fluorided-chlorided silica-titania, sulfatedsilica-titania, fluorided silica-zirconia, chlorided silica-zirconia,bromided silica-zirconia, fluorided-chlorided silica-zirconia, sulfatedsilica-zirconia, fluorided silica-coated alumina, chloridedsilica-coated alumina, bromided silica-coated alumina,fluorided-chlorided silica-coated alumina, sulfated silica-coatedalumina, fluorided mullite, chlorided mullite, bromided mullite,fluorided-chlorided mullite, or sulfated mullite.

In another aspect and in any embodiment of this disclosure, for example,the chemically-treated solid oxide can comprise at least onesilica-coated alumina treated with at least one electron-withdrawinganion, wherein: the at least one silica-coated alumina has a weightratio of alumina to silica in a range from about 1:1 to about 100:1, andthe at least one electron-withdrawing anion comprises fluoride,chloride, bromide, phosphate, triflate, bisulfate, sulfate, or anycombination thereof.

In a further aspect, the chemically-treated solid oxide comprises,consists of, consists essentially of silica-coated alumina that has beenfluorided and chlorided. In this aspect, the silica-coated alumina cancomprise from about 10 to about 80 wt. % silica, based on the weight ofthe silica-coated alumina; the fluorided-chlorided silica-coated aluminacomprises from about 2 to about 15 wt. % F, based on the weight of thefluorided-chlorided silica-coated alumina; and/or thefluorided-chlorided silica-coated alumina comprises from about 1 toabout 10 wt. % Cl, based on the weight of the fluorided-chloridedsilica-coated alumina. In this continuous process, thefluorided-chlorided silica-coated alumina can be produced by a processcomprising: (a) calcining a silica-coated alumina at a peak calciningtemperature to produce a calcined silica-coated alumina; (b) contactingthe calcined silica-coated alumina with a chlorine-containing compoundand calcining at a peak chloriding temperature to produce a chloridedsilica-coated alumina; and (c) contacting the chlorided silica-coatedalumina with a fluorine-containing compound and calcining at a peakfluoriding temperature to produce the fluorided-chlorided silica-coatedalumina. The fluorided-chlorided silica-coated alumina can have, forexample, a pore volume in a range from about 0.9 to about 2.0 mL/g; anda surface area in a range from about 200 to about 700 m²/g.

In yet a further aspect and in any embodiment of this disclosure, thechemically-treated solid oxide can comprise the contact product of atleast one solid oxide compound and at least one electron-withdrawinganion source. The solid oxide compound and electron-withdrawing anionsource are described independently herein and may be utilized in anycombination to further describe the chemically-treated solid oxidecomprising the contact product of at least one solid oxide compound andat least one electron-withdrawing anion source. That is, thechemically-treated solid oxide is provided upon contacting or treatingthe solid oxide with the electron-withdrawing anion source. In anaspect, the solid oxide compound can comprise or can be selected from aninorganic oxide.

In an aspect, the solid oxide compound can be calcined prior tocontacting with the electron-withdrawing anion source, though this isnot required. In another aspect, the solid oxide compound can becalcined during or after contacting with the electron-withdrawing anionsource. Thus, contact product of the solid oxide and theelectron-withdrawing anion may be calcined either during or after thesolid oxide compound is contacted with the electron-withdrawing anionsource. In this aspect, the solid oxide compound may be calcined oruncalcined. In another aspect, the polyanionic solid may comprise thecontact product of at least one calcined solid oxide compound and atleast one electron-withdrawing anion source.

While not intending to be bound by theory, the chemically-treated solidoxide is thought to function as a co-catalyst or activator when used asdisclosed herein. Moreover, the chemically-treated solid oxide isthought to function as a better co-catalyst or activator as compared tothe non-chemically-treated oxide. The activation function of thechemically-treated solid oxide is evident in the enhanced activity ofpolyanionic solid as a whole, as compared to a polyanionic solidcontaining the corresponding untreated solid oxide.

In one aspect, the chemically-treated solid oxide of this disclosure cancomprise a solid inorganic oxide material, a mixed oxide material, or acombination of inorganic oxide materials, that is chemically-treatedwith an electron-withdrawing component, and optionally treated with ametal. Thus, the solid oxide of this disclosure encompasses oxidematerials such as alumina, “mixed oxide” compounds thereof such assilica-alumina, and combinations and mixtures thereof. The mixed oxidecompounds such as silica-alumina can be single or multiple chemicalphases with more than one metal combined with oxygen to form a solidoxide compound, and are encompassed by this disclosure. The solidinorganic oxide material, mixed oxide material, combination of inorganicoxide materials, electron-withdrawing component, and optional metal areindependently described herein and may be utilized in any combination tofurther described the chemically-treated solid oxide.

In one aspect of this disclosure, the chemically-treated solid oxidefurther can comprise a metal or metal ion selected from zinc, nickel,vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum,or any combination thereof; alternatively, the chemically-treated solidoxide further can comprise a metal or metal ion selected from zinc,nickel, vanadium, titanium, or tin, or any combination thereof;alternatively, the chemically-treated solid oxide can further comprise ametal or metal ion selected from zinc, nickel, vanadium, tin, or anycombination thereof.

Examples of chemically-treated solid oxides that further comprise ametal or metal ion include, but are not limited to, zinc-impregnatedchlorided alumina, titanium-impregnated fluorided alumina,zinc-impregnated fluorided alumina, zinc-impregnated chloridedsilica-alumina, zinc-impregnated fluorided silica-alumina,zinc-impregnated sulfated alumina, chlorided zinc aluminate, fluoridedzinc aluminate, sulfated zinc aluminate, or any combination thereof;alternatively, the chemically-treated solid oxide can be selected fromfluorided alumina, chlorided alumina, sulfated alumina, fluoridedsilica-alumina, chlorided silica-alumina, sulfated silica-alumina,fluorided silica-zirconia, sulfated silica-zirconia, or any combinationthereof.

In one aspect, the chemically-treated solid oxide can comprise a solidinorganic oxide comprising oxygen and at least one element selected fromGroup 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 of the periodictable, or comprising oxygen and at least one element selected from thelanthanide or actinide elements; alternatively, the chemically-treatedsolid oxide can comprise a solid inorganic oxide comprising oxygen andat least one element selected from Group 4, 5, 6, 12, 13, or 14 of theperiodic table, or comprising oxygen and at least one element selectedfrom the lanthanide elements. (See: Hawley's Condensed ChemicalDictionary, 11^(th) Ed., John Wiley & Sons; 1995; Cotton, F. A.;Wilkinson, G.; Murillo; C. A.; and Bochmann; M. Advanced InorganicChemistry, 6^(th) Ed., Wiley-Interscience, 1999.) Usually, the inorganicoxide can comprise oxygen and at least one element selected from Al, B,Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti,V, W, P, Y, Zn or Zr; alternatively, the inorganic oxide can compriseoxygen and at least one element selected from Al, B, Si, Ti, P, Zn orZr.

Suitable examples of solid oxide materials or compounds that can be usedin the chemically-treated solid oxide of the present disclosure include,but are not limited to, Al₂O₃, B₂O₃, BeO, Bi₂O₃, CdO, Co₃O₄, Cr₂O₃, CuO,Fe₂O₃, Ga₂O₃, La₂O₃, Mn₂O₃, MoO₃, NiO, P₂O₅, Sb₂O₅, SiO₂, SnO₂, SrO,ThO₂, TiO₂, V₂O₅, WO₃, Y₂O₃, ZnO, ZrO₂, and the like, including mixedoxides thereof, and combinations thereof; alternatively, suitableexamples of solid oxide materials or compounds that can be used in thechemically-treated solid oxide of the present disclosure include, butare not limited to, Al₂O₃, B₂O₃, SiO₂, SnO₂, TiO₂, V₂O₅, WO₃, Y₂O₃, ZnO,ZrO₂, and the like, including mixed oxides thereof, and combinationsthereof; alternatively, suitable examples of solid oxide materials orcompounds that can be used in the chemically-treated solid oxide of thepresent disclosure include, but are not limited to, Al₂O₃, SiO₂, TiO₂.ZrO₂, and the like, including mixed oxides thereof, and combinationsthereof.

Examples of mixed oxides that can be used in the polyanionic solid ofthe present disclosure include, but are not limited to, silica-alumina,silica-titania, silica-zirconia, zeolites, clay minerals, silica-coatedalumina, aluminum phosphate, aluminophosphate, heteropolytungstate,mullite, boehmite, alumina-titania, alumina-zirconia, zinc-aluminate andthe like; alternatively, examples of mixed oxides that can be used inthe polyanionic solid of the present disclosure include, but are notlimited to, silica-alumina, silica-titania, silica-zirconia,alumina-titania, alumina-zirconia, zinc-aluminate and the like;alternatively, examples of mixed oxides that can be used in thepolyanionic solid of the present disclosure include, but are not limitedto, silica-alumina, silica-titania, silica-zirconia, alumina-titania,and the like.

In one aspect of this disclosure, the solid oxide material ischemically-treated by contacting it with at least oneelectron-withdrawing component, typically an electron-withdrawing anionsource. Further, the solid oxide material can be chemically-treated witha metal ion if desired, then calcining to form a metal-containing ormetal-impregnated chemically-treated solid oxide. Alternatively, a solidoxide material and an electron-withdrawing anion source are contactedand calcined simultaneously. The method by which the oxide is contactedwith an electron-withdrawing component, typically a salt or an acid ofan electron-withdrawing anion, includes, but is not limited to, gelling,co-gelling, impregnation of one compound onto another, and the like.Typically, following any contacting method, the contacted mixture ofoxide compound, electron-withdrawing anion, and the metal ion if presentcan be calcined.

Without being bound by theory, the electron-withdrawing component usedto treat the oxide can be any component that increases the Lewis orBrønsted acidity of the solid oxide upon treatment. In one aspect, theelectron-withdrawing component is an electron-withdrawing anion derivedfrom a salt, an acid, or other compound such as a volatile organiccompound that may serve as a source or precursor for that anion.Examples of electron-withdrawing anions include, but are not limited to,sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate,fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate,fluorozirconate, fluorotitanate, trifluoroacetate, triflate, and thelike, including mixtures and combinations thereof; alternatively,examples of electron-withdrawing anions include, but are not limited to,sulfate, bisulfate, fluoride, chloride, fluorosulfate, fluoroborate,phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, and the like, including mixtures and combinationsthereof; alternatively, examples of electron-withdrawing anions include,but are not limited to, fluoride, sources of fluoride, chloride,bisulfate, sulfate, and the like, including mixtures and combinationsthereof. In addition, other ionic or non-ionic compounds that serve assources for these electron-withdrawing anions may also be employed inthe present disclosure.

When the electron-withdrawing component can comprise a salt of anelectron-withdrawing anion, the counterion or cation of that salt may beselected from any cation that allows the salt to revert or decomposeback to the acid during calcining. Factors that dictate the suitabilityof the particular salt to serve as a source for the electron-withdrawinganion include, but are not limited to, the solubility of the salt in thedesired solvent, the lack of adverse reactivity of the cation,ion-pairing effects between the cation and anion, hygroscopic propertiesimparted to the salt by the cation, and the like, and thermal stabilityof the anion. Examples of suitable cations in the salt of theelectron-withdrawing anion include, but are not limited to, ammonium,trialkyl ammonium, tetraalkyl ammonium, tetraalkyl phosphonium, H⁺,[H(OEt₂)₂]⁺, and the like; alternatively, ammonium; alternatively,trialkyl ammonium; alternatively, tetraalkyl ammonium; alternatively,tetraalkyl phosphonium; or alternatively, H⁺, [H(OEt₂)₂]⁺.

Further, combinations of one or more different electron withdrawinganions, in varying proportions, can be used to tailor the specificactivity of the chemically-treated solid oxide to the desired level.Combinations of electron withdrawing components may be contacted withthe oxide material simultaneously or individually, and any order thataffords the desired chemically-treated solid oxide acidity. For example,one aspect of this disclosure is employing two or moreelectron-withdrawing anion source compounds in two or more separatecontacting steps. Thus, one example of such a process by which anchemically-treated solid oxide is prepared is as follows: a selectedsolid oxide compound, or combination of oxide compounds, is contactedwith a first electron-withdrawing anion source compound to form a firstmixture, this first mixture is then calcined, the calcined first mixtureis then contacted with a second electron-withdrawing anion sourcecompound to form a second mixture, followed by calcining said secondmixture to form a treated solid oxide compound. In such a process, thefirst and second electron-withdrawing anion source compounds aretypically different compounds, although they may be the same compound.

In one aspect of the disclosure, the chemically-treated solid oxide maybe produced by a process comprising:

-   -   1) contacting a solid oxide compound with at least one        electron-withdrawing anion source compound to form a first        mixture; and    -   2) calcining the first mixture to form the chemically-treated        solid oxide.

In another aspect of this disclosure, the chemically-treated solid oxidecan be produced by a process comprising:

-   -   1) contacting at least one solid oxide compound with a first        electron-withdrawing anion source compound to form a first        mixture; and    -   2) calcining the first mixture to produce a calcined first        mixture;    -   3) contacting the calcined first mixture with a second        electron-withdrawing anion source compound to form a second        mixture; and    -   4) calcining the second mixture to form the chemically-treated        solid oxide.        Thus, the solid oxide activator-support is sometimes referred to        simply as a treated solid oxide compound.

In one aspect of this disclosure, once the solid oxide has been treatedand dried, it may be subsequently calcined. Calcining of the chemicallytreated solid oxide is generally conducted in an ambient atmosphere;alternatively, in a dry ambient atmosphere. The solid oxide may becalcined at a temperature from about 200° C. to about 900° C.;alternatively, from about 300° C. to about 800° C.; alternatively, fromabout 400° C. to about 700° C.; or alternatively, from about 350° C. toabout 550° C. The period of time at which the solid oxide is maintainedat the calcining temperature may be about 1 minute to about 100 hours;alternatively, from about 1 hour to about 50 hours; alternatively, fromabout 3 hours to about 20 hours; or alternatively, from about 1 to about10 hours.

Further, any type of suitable ambient atmosphere can be used duringcalcining. Generally, calcining is conducted in an oxidizing atmosphere,such as air. Alternatively, an inert atmosphere, such as nitrogen orargon, or a reducing atmosphere such as hydrogen or carbon monoxide, maybe used.

In another aspect of the disclosure, the solid oxide component used toprepare the chemically-treated solid oxide has a pore volume greaterthan about 0.1 cc/g. In another aspect, the solid oxide component has apore volume greater than about 0.5 cc/g, and in yet another aspect,greater than about 1.0 cc/g. In still another aspect, the solid oxidecomponent has a surface area from about 100 to about 1000 m²/g. Inanother aspect, solid oxide component has a surface area from about 200to about 800 m²/g, and in still another aspect, from about 250 to about600 m²/g.

The solid oxide material may be treated with a source of halide ion orsulfate ion, or a combination of anions, and optionally treated with ametal ion, then calcined to provide the chemically-treated solid oxidein the form of a particulate solid. In one aspect, the solid oxidematerial is treated with a source of sulfate, termed a sulfating agent,a source of chloride ion, termed a chloriding agent, a source offluoride ion, termed a fluoriding agent, or a combination thereof, andcalcined to provide the solid oxide activator.

In one aspect of this disclosure, the chemically-treated solid oxide cancomprise a fluorided solid oxide in the form of a particulate solid,thus a source of fluoride ion is added to the oxide by treatment with afluoriding agent. In still another aspect, fluoride ion may be added tothe oxide by forming a slurry of the oxide in a suitable solvent such asalcohol or water, including, but are not limited to, the one to threecarbon alcohols because of their volatility and low surface tension.Examples of fluoriding agents that can be used in this disclosureinclude, but are not limited to, hydrofluoric acid (HF), ammoniumfluoride (NH₄F), ammonium bifluoride (NH₄HF₂), ammoniumtetrafluoroborate (NH₄BF₄), ammonium silicofluoride (hexafluorosilicate)((NH₄)₂SiF₆), ammonium hexafluorophosphate (NH₄PF₆), analogs thereof,and combinations thereof; alternatively, hydrofluoric acid (HF),ammonium fluoride (NH₄F), ammonium bifluoride (NH₄HF₂), ammoniumtetrafluoroborate (NH₄BF₄), analogs thereof, and combinations thereof.For example, ammonium bifluoride NH₄HF₂ may be used as the fluoridingagent, due to its ease of use and ready availability.

In another aspect of the present disclosure, the solid oxide can betreated with a fluoriding agent during the calcining step. Anyfluoriding agent capable of thoroughly contacting the solid oxide duringthe calcining step can be used. For example, in addition to thosefluoriding agents described previously, volatile organic fluoridingagents may be used. Examples of volatile organic fluoriding agentsuseful in this aspect of the disclosure include, but are not limited to,freons, perfluorohexane, perfluorobenzene, fluoromethane,trifluoroethanol, and combinations thereof. Gaseous hydrogen fluoride orfluorine itself can also be used with the solid oxide is fluoridedduring calcining. One convenient method of contacting the solid oxidewith the fluoriding agent is to vaporize a fluoriding agent into a gasstream used to fluidize the solid oxide during calcination.

Similarly, in another aspect of this disclosure, the chemically-treatedsolid oxide can comprise a chlorided solid oxide in the form of aparticulate solid, thus a source of chloride ion is added to the oxideby treatment with a chloriding agent. The chloride ion may be added tothe oxide by forming a slurry of the oxide in a suitable solvent. Inanother aspect of the present disclosure, the solid oxide can be treatedwith a chloriding agent during the calcining step. Any chloriding agentcapable of serving as a source of chloride and thoroughly contacting theoxide during the calcining step can be used. For example, volatileorganic chloriding agents may be used. Examples of volatile organicchloriding agents useful in this aspect of the disclosure include, butare not limited to, certain freons, perchlorobenzene, chloromethane,dichloromethane, chloroform, carbon tetrachloride, trichloroethanol, orany combination thereof. Gaseous hydrogen chloride or chlorine itselfcan also be used with the solid oxide during calcining. One convenientmethod of contacting the oxide with the chloriding agent is to vaporizea chloriding agent into a gas stream used to fluidize the solid oxideduring calcination.

In one aspect, the amount of fluoride or chloride ion present beforecalcining the solid oxide is generally from about 2 to about 50% byweight, where the weight percents are based on the weight of the solidoxide, for example silica-alumina, before calcining. In another aspect,the amount of fluoride or chloride ion present before calcining thesolid oxide is from about 3 to about 25% by weight, and in anotheraspect, from about 4 to about 20% by weight. Once impregnated withhalide, the halided oxide may be dried by any method known in the artincluding, but not limited to, suction filtration followed byevaporation, drying under vacuum, spray drying, and the like, althoughit is also possible to initiate the calcining step immediately withoutdrying the impregnated solid oxide.

In an aspect, silica-alumina may be utilized as the solid oxidematerial. The silica-alumina used to prepare the treated silica-aluminacan have a pore volume greater than about 0.5 cc/g. In one aspect, thepore volume may be greater than about 0.8 cc/g, and in another aspect,the pore volume may be greater than about 1.0 cc/g. Further, thesilica-alumina may have a surface area greater than about 100 m²/g. Inone aspect, the surface area is greater than about 250 m²/g, and inanother aspect, the surface area may be greater than about 350 m²/g.Generally, the silica-alumina of this disclosure has an alumina contentfrom about 5 to about 95%. In one aspect, the alumina content of thesilica-alumina may be from about 5 to about 50%, and in another aspect,the alumina content of the silica-alumina may be from about 8% to about30% alumina by weight. In yet another aspect, the solid oxide componentcan comprise alumina without silica and in another aspect, the solidoxide component can comprise silica without alumina.

The sulfated solid oxide can comprise sulfate and a solid oxidecomponent such as alumina or silica-alumina, in the form of aparticulate solid. The sulfated oxide can be further treated with ametal ion if desired such that the calcined sulfated oxide can comprisea metal. In one aspect, the sulfated solid oxide can comprise sulfateand alumina. In one aspect of this disclosure, the sulfated alumina isformed by a process wherein the alumina is treated with a sulfatesource, for example selected from, but not limited to, sulfuric acid ora sulfate salt such as ammonium sulfate. In one aspect, this process maybe performed by forming a slurry of the alumina in a suitable solventsuch as alcohol or water, in which the desired concentration of thesulfating agent has been added. Suitable organic solvents include, butare not limited to, the one to three carbon alcohols because of theirvolatility and low surface tension.

In one aspect of the disclosure, the amount of sulfate ion presentbefore calcining is generally from about 0.5 parts by weight to about100 parts by weight sulfate ion to about 100 parts by weight solidoxide. In another aspect, the amount of sulfate ion present beforecalcining is generally from about 1 part by weight to about 50 parts byweight sulfate ion to about 100 parts by weight solid oxide, and instill another aspect, from about 5 parts by weight to about 30 parts byweight sulfate ion to about 100 parts by weight solid oxide. Theseweight ratios are based on the weight of the solid oxide beforecalcining. Once impregnated with sulfate, the sulfated oxide may bedried by any method known in the art including, but not limited to,suction filtration followed by evaporation, drying under vacuum, spraydrying, and the like, although it is also possible to initiate thecalcining step immediately.

In addition to being treated with an electron-withdrawing component (forexample, halide or sulfate ion), the solid inorganic oxide of thisdisclosure can be treated with a metal source if desired, includingmetal salts or metal-containing compounds. In one aspect of thedisclosure, these compounds may be added to or impregnated onto thesolid oxide in solution form, and subsequently converted into thesupported metal upon calcining. The solid oxide may be treated withmetal salts or metal-containing compounds before, after, or at the sametime that the solid oxide is treated with the electron-withdrawinganion.

Further, any method of impregnating the solid oxide material with ametal may be used. The method by which the oxide is contacted with ametal source, typically a salt or metal-containing compound, includes,but is not limited to, gelling, co-gelling, impregnation of one compoundonto another, and the like. Following any contacting method, thecontacted mixture of oxide compound, electron-withdrawing anion, and themetal ion is typically calcined. Alternatively, a solid oxide material,an electron-withdrawing anion source, and the metal salt ormetal-containing compound are contacted and calcined simultaneously.

Various processes to prepare solid oxide activator-supports that can beemployed in this disclosure have been reported. For example, U.S. Pat.Nos. 6,107,230, 6,165,929, 6,294,494, 6,300,271, 6,316,553, 6,355,594,6,376,415, 6,391,816, 6,395,666, 6,524,987, 6,548,441, 6,750,302,6,831,141, 6,936,667, 6,992,032, 7,601,665, 7,026,494, 7,148,298,7,470,758, 7,517,939, 7,576,163, 7,294,599, 7,629,284, 7,501,372,7,041,617, 7,226,886, 7,199,073, 7,312,283, 7,619,047, 7,884,163,8,703,886, and 9,023,959 describe such methods, each of which isincorporated by reference herein, in pertinent part.

Organic Base on Solid Support as Polyanionic Solids

In one aspect, this disclosure encompasses a continuous process asdescribed herein, in which the polyanionic solid (also termed anactivator or co-catalyst) can comprise an organic base on a solidsupport. In this aspect, for example, the polyanionic solid cancomprise, consists of, consists essentially of, or be selected from anorganic base moiety immobilized on a solid support. For example, theorganic base moiety immobilized on a solid support comprises structuralunits having the general formula (I):

SS-[A]_(x)-L-B  (I);

wherein SS is a solid support, A is an anchor moiety, L is a direct bondor linking moiety, and B is an organic base moiety, and wherein x is 0to 3. In an aspect, the organic base moiety B has the general formula:

[—CR¹R²—O]⁻, [—CR¹R²—S]⁻, [—CR¹R²—NR³]⁻, or [—CR¹R²—PR³]⁻,

wherein each of R¹ and R², independently or together, are selected fromH or an unbranched or branched, acyclic or cyclic, C₁-C₁₂ hydrocarbylresidue; and R³ is selected independently from hydrogen or a substitutedor an unsubstituted C₁-C₁₂ hydrocarbyl. Each of R¹ and R², independentlyor together, can be selected from H, methyl, ethyl, 1-propyl, 2-propyl,1-butyl, 2-butyl, tert-butyl, 1-(2-methyl) propyl, 2-(2-methyl)propyl,1-pentyl, 1-(2-methyl)pentyl, 1-hexyl, 1-(2-ethyl)hexyl, 1-heptyl,1-(2-propyl)heptyl, 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl,adamantyl, cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl,cycloheptyl, cyclooctyl, norbornyl, phenyl, napthyl, tolyl, or xylyl.

In a further aspect, the organic base moiety B of the general formulaSS-[A]_(x)-L-B (I) can have the formula:

wherein Y is selected from a halide or a C₁-C₆ hydrocarbyl, and m is0-4; and

wherein

is the SS-[A]_(x)-L portion of formula (I).

According to this aspect, the organic base moiety immobilized on a solidsupport can have the following structure:

According to a further aspect, the organic base moiety B of the generalformula SS-[A]_(x)-L-B (I) can have the formula:

wherein Y is selected from a halide or a C₁-C₆ hydrocarbyl, m is 0-4,and R⁶ is selected from a C₁-C₆ alkyl or aryl; and

wherein

is the SS-[A]_(x)-L portion of formula (I).

According to this aspect, the organic base moiety immobilized on a solidsupport can have the following structure:

In a further aspect of the continuous process according to thisdisclosure, the organic base moiety immobilized on a solid support canhave the general formula (II):

SS-[O]_(3-n)—Si(OR⁴)_(n)—B  (II);

wherein n is 0, 1, or 2, and each R⁴ is selected independently from asubstituted or an unsubstituted C₁-C₁₂ hydrocarbyl.

The continuous process can also encompass use of an organic baseimmobilized on a solid support which can comprise structural unitshaving the general formula (I):

SS-[A]_(x)-L-B  (I);

wherein the organic base moiety B is selected from [—CR¹R²—O]⁻,[—CR¹R²—S]⁻, [—CR¹R²—NR³]⁻, or [—CR¹R²—PR³]⁻, wherein each of R¹ and R²,independently or together, are selected from H or an unbranched orbranched, acyclic or cyclic, C₁-C₁₂ hydrocarbyl residue; and R³ isselected independently from hydrogen or a substituted or anunsubstituted C₁-C₁₂ hydrocarbyl; and

A is selected from [—YR⁵R⁶—CH₂], wherein

-   -   a) Y is N⁺ or C, and R⁵ and R⁶ are selected independently from        hydrogen, or a substituted or an unsubstituted C₁-C₁₂        hydrocarbyl, or    -   b) Y is Si, and R⁵ and R⁶ are selected independently from a        substituted or an unsubstituted C₁-C₁₂ hydrocarbyl, or a        substituted or an unsubstituted C₁-C₁₂ hydrocarbyloxide.        A further aspect is that combinations of any of these organic        base moieties immobilized on at least one solid support are        encompassed by this disclosure.

Metal Acrylate Release and Polyanionic Solid Regeneration

In the example of Scheme 1, the polyanionic solid can be a metalpoly(4-vinylphenoxide), which is formed upon the reaction of the neutralpolymer 5, for example poly(4-vinylphenol), with a base 7 such as ametal-containing base. For example, the metal in a metal-containing basecan be, but is not limited to, a metal of Groups 1, 2, 12 or 13, such aslithium, sodium, potassium, rubidium, cesium, magnesium, calcium, zinc,aluminum or gallium. As illustrated in Scheme 1, the reaction of thepolyanionic solid 3 and metalalactone 2 (for example, through anintermediate represented generally as 4) both eliminates or releases themetal acrylate 6 from 4 and regenerates catalyst compound 1 andbyproduct neutral polymer 5 (e.g. poly(4-vinylphenol) in Scheme 1),which is regenerated to the polyanionic solid reactant upon its reactionwith a regenerative base 7. Various bases 7 can be used according tothis disclosure.

The step of regenerating the polyanionic solid can be effected bycontacting the polyanionic solid with a regenerative base 7 comprising ametal cation following the formation of the α,β-unsaturated carboxylicacid or a salt thereof. A wide range of bases 7 can be used for thisregeneration step. For example, the regenerative base 7 can be or cancomprise metal-containing bases which can include any reactive inorganicbasic metal compound or mixture of compounds that contain metal cationsor cation sources, for example, alkali and alkaline earth metalcompounds such as oxides, hydroxides, alkoxides, aryloxides, amides,alkyl amides, arylamides, and carbonates. Suitable bases include orcomprise, for example, carbonates (e.g., Na₂CO₃, Cs₂CO₃, MgCO₃),hydroxides (e.g., Mg(OH)₂, Ca(OH)₂, NaOH, KOH), alkoxides (e.g.,Al(O^(i)Pr)₃, Na(O^(t)Bu), Mg(OEt)₂), aryloxides (e.g. Na(OC₆H₅), sodiumphenoxide) and the like. Typically, this regeneration step furthercomprising or is followed by the step of washing the polyanionic solidwith a solvent or the diluent.

According to an aspect, the regenerative base 7 can be or can comprise anucleophilic base, for example a metal hydroxide or metal alkoxide.While the regenerative base 7 can comprise a non-nucleophilic base, theprocesses disclosed herein work in the absence of a non-nucleophilicbase such an alkali metal hydride or an alkaline earth metal hydride, analkali metal or alkaline earth metal dialkylamides and diarylamides, analkali metal or alkaline earth metal hexalkyldisilazane, and an alkalimetal or alkaline earth metal dialkylphosphides and diarylphosphides.

Typically, the inorganic bases such as alkali metal hydroxides or alkalimetal alkoxides have been found to work the best. However, in oneaspect, the reaction of Scheme 1 can be conducted using some bases butin the absence of certain other organic bases such as an alkoxide,aryloxide, amide, alkyl amide, arylamide, or the like. In anotheraspect, the polyanionic solid (and associated cations) can be used andregenerated in the absence of an alkoxide or aryloxide. Further, thereactions and processes disclosed herein can be conducted in the absenceof an alkoxide, an aryloxide, an alkylamide, an arylamide, an amine, ahydride, a phosphazene, and/or substituted analogs thereof. For example,the processes disclosed herein can be conducted in the absence of sodiumhydride, an aryloxide salt (such as a sodium aryloxide), an alkoxidesalt (such as a sodium tert-butoxide), and/or a phosphazene.

Diluents

The processes disclosed herein typically are conducted in the presenceof a diluent. Mixtures and combinations of diluents can be utilized inthese processes. The diluent can comprise, consist essentially of, orconsist of, any suitable solvent or any solvent disclosed herein, unlessotherwise specified. For example, the diluent can comprise, consistessentially of, or consist of a non-protic solvent, a protic solvent, anon-coordinating solvent, or a coordinating solvent. For instance, inaccordance with one aspect of this disclosure, the diluent can comprisea non-protic solvent. Representative and non-limiting examples ofnon-protic solvents can include tetrahydrofuran (THF), 2,5-Me₂THF,acetone, toluene, chlorobenzene, pyridine, acetonitrile, carbon dioxide,olefin and the like, as well as combinations thereof. In accordance withanother aspect, the diluent can comprise a weakly coordinating ornon-coordinating solvent. Representative and non-limiting examples ofweakly coordinating or non-coordinating solvents can include toluene,chlorobenzene, paraffins, halogenated paraffins, and the like, as wellas combinations thereof.

In accordance with yet another aspect, the diluent can comprise acarbonyl-containing solvent, for instance, ketones, esters, amides, andthe like, as well as combinations thereof. Representative andnon-limiting examples of carbonyl-containing solvents can includeacetone, ethyl methyl ketone, ethyl acetate, propyl acetate, butylacetate, isobutyl isobutyrate, methyl lactate, ethyl lactate,N,N-dimethylformamide, and the like, as well as combinations thereof. Instill another aspect, the diluent can comprise THF, 2,5-Me₂THF,methanol, acetone, toluene, chlorobenzene, pyridine, anisole, or acombination thereof; alternatively, THF; alternatively, 2,5-Me₂THF;alternatively, methanol; alternatively, acetone; alternatively, toluene;alternatively, chlorobenzene; or alternatively, pyridine.

In an aspect, the diluent can comprise (or consist essentially of, orconsist of) an aromatic hydrocarbon solvent. Non-limiting examples ofsuitable aromatic hydrocarbon solvents that can be utilized singly or inany combination include benzene, toluene, xylene (inclusive ofortho-xylene, meta-xylene, para-xylene, or mixtures thereof), andethylbenzene, or combinations thereof; alternatively, benzene;alternatively, toluene; alternatively, xylene; or alternatively,ethylbenzene.

In an aspect, the diluent can comprise (or consist essentially of, orconsist of) a halogenated aromatic hydrocarbon solvent. Non-limitingexamples of suitable halogenated aromatic hydrocarbon solvents that canbe utilized singly or in any combination include chlorobenzene,dichlorobenzene, and combinations thereof; alternatively, chlorobenzene;or alternatively, dichlorobenzene.

In an aspect, the diluent can comprise (or consist essentially of, orconsist of) an ether solvent. Non-limiting examples of suitable ethersolvents that can be utilized singly or in any combination includedimethyl ether, diethyl ether, diisopropyl ether, di-n-propyl ether,di-n-butyl ether, diphenyl ether, methyl ethyl ether, methyl t-butylether, dihydrofuran, tetrahydrofuran (THF), 2,5-Me₂THF,1,2-dimethoxyethane, 1,4-dioxane, anisole, and combinations thereof;alternatively, diethyl ether, dibutyl ether, THF, 2,5-Me₂THF,1,2-dimethoxyethane, 1,4-dioxane, and combinations thereof;alternatively, THF; or alternatively, diethyl ether.

In a further aspect, any of these aforementioned diluents can beexcluded from the diluent or diluent mixture. For example, the diluentcan be absent a phenol or a substituted phenol, an alcohol or asubstituted alcohol, an amine or a substituted amine, water, an ether,an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, analdehyde or ketone, an ester or amide, and/or absent a halogenatedaromatic hydrocarbon, or any substituted analogs of these diluentshalogenated analogs, including any of the aforementioned diluents.Therefore, Applicant reserves the right to exclude any of the diluentsprovided herein.

The diluent can comprise carbon dioxide, and can also comprise CO₂ underpressure. The diluent also can comprise the α,β-unsaturated carboxylicacid or the salt thereof, formed in the process. The diluent cancomprise any suitable non-protic solvent, any non-protic solventdisclosed herein, and/or carbon dioxide (CO₂) under pressure. Thediluent can comprise any suitable non-protic solvent, any non-proticsolvent disclosed herein, the olefin such as ethylene, and/or carbondioxide (CO₂) under pressure. Specifically, the diluent can comprise theolefin such as ethylene and carbon dioxide (CO₂) under pressure. Thediluent also can comprise any suitable weakly coordinating ornon-coordinating solvent, or any weakly coordinating or non-coordinatingsolvent disclosed herein.

In all aspects and embodiments disclosed herein, the diluent can includeor comprise carbon dioxide, olefin, or combinations thereof. At least aportion of the diluent can comprise the α,β-unsaturated carboxylic acidor the salt thereof, formed in the process.

Transition Metal Compounds and Ligands

In this disclosure, the term transition metal precursor, transitionmetal compound, transition metal catalyst, transition metal precursorcompound, carboxylation catalyst, transition metal precursor complex andsimilar terms refer to a chemical compound that serves as the precursorto the metalalactone, prior to the coupling of the olefin and carbondioxide at the metal center of the transition metal precursor compound.Therefore, the metal of the transition metal precursor compound and themetal of the metalalactone are the same. In some aspects, some of theligands of the transition metal precursor compound carry over and areretained by the metalalactone following the coupling reaction. In otheraspects, the transition metal precursor compound loses its existingligands, referred to herein as first ligands, in presence of additionalligands such as chelating ligands, referred to herein as second ligands,as the metalalactone is formed. Therefore, the metalalactone generallyincorporates the second (added) ligand(s), though in some aspects, themetalalactone can comprise the first ligand(s) that were bound in thetransition metal precursor compound.

According to an aspect, the transition metal catalyst or compound usedin the processes can be used without being immobilized on a solidsupport. That is the transition metal catalyst can be used is its usualform which is soluble in most useful solvents, without being bonded toor supported on any insoluble support, such as an inorganic oxide ormixed oxide material.

A prototypical example of a transition metal precursor compound thatloses its initial ligands in the coupling reaction in the presence of asecond (added) ligand, wherein the metalalactone incorporates the second(added) ligand(s), is contacting Ni(COD)₂ (COD is 1,5-cyclooctadiene)with a diphosphine ligand such as 1,2-bis(dicyclohexylphosphino)ethanein a diluent in the presence of ethylene and CO₂ to form anickelalactone with a coordinated 1,2-bis(dicyclohexylphosphino)ethanebidentate ligand.

Accordingly, in an aspect, the process for producing an α,β-unsaturatedcarboxylic acid or a salt thereof, can comprise (1) contacting in anyorder: (a) a transition metal precursor compound comprising at least onefirst ligand; (b) optionally, at least one second ligand; (c) an olefin;(d) carbon dioxide (CO₂); (e) a diluent; and (f) an polyanionic solidcomprising associated metal cations to provide a reaction mixture; and(2) applying reaction conditions to the reaction mixture suitable toform the α,β-unsaturated carboxylic acid or a salt thereof.

Generally, the processes disclosed herein employ a metalalactone or atransition metal precursor compound or complex. The transition metal ofthe metalalactone, or of the transition metal precursor compound, can bea Group 3 to Group 8 transition metal or, alternatively, a Group 8 toGroup 11 transition metal. In one aspect, for instance, the transitionmetal can be Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, or Au, while inanother aspect, the transition metal can be Fe, Ni, or Rh.Alternatively, the transition metal can be Fe; alternatively, thetransition metal can be Co; alternatively, the transition metal can beNi; alternatively, the transition metal can be Cu; alternatively, thetransition metal can be Ru; alternatively, the transition metal can beRh; alternatively, the transition metal can be Pd; alternatively, thetransition metal can be Ag; alternatively, the transition metal can beIr; alternatively, the transition metal can be Pt; or alternatively, thetransition metal can Au.

In particular aspects contemplated herein, the transition metal can beNi. Hence, the metalalactone can be a nickelalactone and the transitionmetal precursor compound can be a Ni-ligand complex in these aspects.

The ligand of the metalalactone and/or of the transition metal precursorcompound, can be any suitable neutral electron donor group and/or Lewisbase. For instance, the suitable neutral ligands can include sigma-donorsolvents that contain a coordinating atom (or atoms) that can coordinateto the transition metal of the metalalactone (or of the transition metalprecursor compound). Examples of suitable coordinating atoms in theligands can include, but are not limited to, O, N, S, and P, orcombinations of these atoms. In some aspects consistent with thisdisclosure, the ligand can be a bidentate ligand.

In an aspect, the ligand used to form the metalalactone and/or thetransition metal precursor compound can be an ether, an organiccarbonyl, a thioether, an amine, a nitrile, or a phosphine. In anotheraspect, the ligand used to form the metalalactone or the transitionmetal precursor compound can be an acyclic ether, a cyclic ether, anacyclic organic carbonyl, a cyclic organic carbonyl, an acyclicthioether, a cyclic thioether, a nitrile, an acyclic amine, a cyclicamine, an acyclic phosphine, or a cyclic phosphine.

Suitable ethers can include, but are not limited to, dimethyl ether,diethyl ether, dipropyl ether, dibutyl ether, methyl ethyl ether, methylpropyl ether, methyl butyl ether, diphenyl ether, ditolyl ether,tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran,2,3-dihydrofuran, 2,5-dihydrofuran, furan, benzofuran, isobenzofuran,dibenzofuran, tetrahydropyran, 3,4-dihydro-2H-pyran,3,6-dihydro-2H-pyran, 2H-pyran, 4H-pyran, 1,3-dioxane, 1,4-dioxane,morpholine, and the like, including substituted derivatives thereof.

Suitable organic carbonyls can include ketones, aldehydes, esters, andamides, either alone or in combination, and illustrative examples caninclude, but are not limited to, acetone, acetophenone, benzophenone,N,N-dimethylformamide, N,N-dimethylacetamide, methyl acetate, ethylacetate, and the like, including substituted derivatives thereof.

Suitable thioethers can include, but are not limited to, dimethylthioether, diethyl thioether, dipropyl thioether, dibutyl thioether,methyl ethyl thioether, methyl propyl thioether, methyl butyl thioether,diphenyl thioether, ditolyl thioether, thiophene, benzothiophene,tetrahydrothiophene, thiane, and the like, including substitutedderivatives thereof.

Suitable nitriles can include, but are not limited to, acetonitrile,propionitrile, butyronitrile, benzonitrile, 4-methylbenzonitrile, andthe like, including substituted derivatives thereof.

Suitable amines can include, but are not limited to, methyl amine, ethylamine, propyl amine, butyl amine, dimethyl amine, diethyl amine,dipropyl amine, dibutyl amine, trimethyl amine, triethyl amine,tripropyl amine, tributyl amine, aniline, diphenylamine, triphenylamine,tolylamine, xylylamine, ditolylamine, pyridine, quinoline, pyrrole,indole, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine,2,5-dimethylpyrrole, 2,5-diethylpyrrole, 2,5-dipropylpyrrole,2,5-dibutylpyrrole, 2,4-dimethylpyrrole, 2,4-diethylpyrrole,2,4-dipropylpyrrole, 2,4-dibutylpyrrole, 3,4-dimethylpyrrole,3,4-diethylpyrrole, 3,4-dipropylpyrrole, 3,4-dibutylpyrrole,2-methylpyrrole, 2-ethylpyrrole, 2-propylpyrrole, 2-butylpyrrole,3-methylpyrrole, 3-ethylpyrrole, 3-propylpyrrole, 3-butylpyrrole,3-ethyl-2,4-dimethylpyrrole, 2,3,4,5-tetramethylpyrrole,2,3,4,5-tetraethylpyrrole, 2,2′-bipyridine,1,8-Diazabicyclo[5.4.0]undec-7-ene, di(2-pyridyl)dimethylsilane,N,N,N′,N′-tetramethylethylenediamine, 1,10-phenanthroline,2,9-dimethyl-1,10-phenanthroline, glyoxal-bis(mesityl)-1,2-diimine andthe like, including substituted derivatives thereof. Suitable amines canbe primary amines, secondary amines, or tertiary amines.

Suitable phosphines and other phosphorus compounds can include, but arenot limited to, trimethylphosphine, triethylphosphine,tripropylphosphine, tributylphosphine, phenylphosphine, tolylphosphine,diphenylphosphine, ditolylphosphine, triphenylphosphine,tritolylphosphine, methyldiphenylphosphine, dimethylphenylphosphine,ethyldiphenylphosphine, diethylphenylphosphine, tricyclohexylphosphine,trimethyl phosphite, triethyl phosphite, tripropyl phosphite,triisopropyl phosphite, tributyl phosphite and tricyclohexyl phosphite,2-(di-t-butylphosphino)biphenyl, 2-di-t-butylphosphino-1,1′-binaphthyl,2-(di-t-butylphosphino)-3,6-dimethoxy-2′,4′,6′-tri-i-propyl-1,1′-biphenyl,2-di-t-butylphosphino-2′-methylbiphenyl,2-(di-t-butylphosphinomethyl)pyridine,2-di-t-butylphosphino-2′,4′,6′-tri-i-propyl-1,1′-biphenyl,2-(dicyclohexylphosphino)biphenyl,(S)-(+)-(3,5-dioxa-4-phospha-cyclohepta[2,1-a;3,4-a′]dinaphthalen-4-yl)dimethylamine,2-(diphenylphosphino)-2′-methoxy-1,1′-binaphthyl,1,2,3,4,5-pentaphenyl-1′-(di-t-butylphosphino)ferrocene,2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP),1,2-bis(dimethylphosphino)ethane, 1,2-bis(diethylphosphino)ethane,1,2-bis(dipropylphosphino)-ethane, 1,2-bis(diisopropylphosphino)ethane,1,2-bis(dibutyl-phosphino)ethane, 1,2-bis(di-t-butyl-phosphino)ethane,1,2-bis(dicyclohexylphosphino)ethane,1,3-bis(dicyclohexylphosphino)propane,1,3-bis(diisopropylphosphino)propane, 1,3-bis(diphenylphosphino)propane,1,3-bis(di-t-butylphosphino)propane,1,4-bis(diisopropylphosphino)butane, 1,4-bis(diphenylphosphino)butane,2,2′-bis[bis(3,5-dimethylphenyl)phosphino]-4,4′,6,6′-tetramethoxybiphenyl,2,6-bis(di-t-butylphosphinomethyl)pyridine,2,2′-bis(dicyclohexylphosphino)-1,1′-biphenyl,bis(2-dicyclohexylphosphinophenyl)ether,5,5′-bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole,2-t-butylphosphinomethylpyridine, bis(diphenylphosphino)ferrocene,bis(diphenylphosphino)methane, bis(dicyclohexylphosphino)methane,bis(di-t-butylphosphino)methane, and the like, including substitutedderivatives thereof.

In other aspects, the ligand used to form the metalalactone or thetransition metal precursor compound can be a carbene, for example, aN-heterocyclic carbene (NHC) compound. Representative and non-limitingexamples of suitable N-heterocyclic carbene (NHC) materials include thefollowing:

Illustrative and non-limiting examples of metalalactone complexes(representative nickelalactones) suitable for use as described hereininclude the following compounds (Cy=cyclohexyl, ^(t)Bu=tert-butyl):

The transition metal precursor compounds corresponding to theseillustrative metalalactones are shown below:

Metalalactones can be synthesized according to the following generalreaction scheme (illustrated with nickel as the transition metal;Ni(COD)₂ is bis(1,5-cyclooctadiene)nickel(0)):

and according to suitable procedures well known to those of skill in theart.

Suitable ligands, transition metal precursor compounds, andmetalalactones are not limited solely to those ligands, transition metalprecursor compounds, and metalalactones disclosed herein. Other suitableligands, transition metal precursor compounds, and metalalactones aredescribed, for example, in U.S. Pat. Nos. 7,250,510, 8,642,803, and8,697,909; Journal of Organometallic Chemistry, 1983, 251, C51-C53; Z.Anorg. Allg. Chem., 1989, 577, 111-114; Journal of OrganometallicChemistry, 2004, 689, 2952-2962; Organometallics, 2004, Vol. 23,5252-5259; Chem. Commun., 2006, 2510-2512; Organometallics, 2010, Vol.29, 2199-2202; Chem. Eur. J., 2012, 18, 14017-14025; Organometallics,2013, 32 (7), 2152-2159; and Chem. Eur. J., 2014, Vol. 20, 11,3205-3211; the disclosures of which are incorporated herein by referencein their entirety.

The following references provide information related to the structureand/or activity relationships in the olefin and CO₂ coupling process, asobserved by changes in phenoxide structure, the phosphine ligandstructure, and other ligand structures: Manzini, S.; Huguet, N.; Trapp,O.; Schaub, T. Eur. J. Org. Chem. 2015, 7122; and Al-Ghamdi, M.;Vummaleti, S. V. C.; Falivene, L.; Pasha, F. A.; Beetstra, D. J.;Cavallo, L. Organometallics 2017, 36, 1107-1112. These references areincorporated herein by reference in their entireties.

Generally, the features of the processes disclosed herein (e.g., themetalalactone, the diluent, the polyanionic solid, the α,β-unsaturatedcarboxylic acid or salt thereof, the transition metal precursorcompound, the olefin, and the reaction conditions under which theα,β-unsaturated carboxylic acid, or a salt thereof, is formed, amongothers) are independently described, and these features can be combinedin any combination to further describe the disclosed processes.

Continuous Process and Reaction Methods

This disclosure provides a continuous process for producing anα,β-unsaturated carboxylic acid or salt thereof. In an aspect, thecontinuous process for producing an α,β-unsaturated carboxylic acid orsalt thereof, the process can comprise:

-   -   1) in a first stage, contacting (a) a transition metal precursor        compound comprising at least one first ligand, (b) optionally,        at least one second ligand, (c) an olefin, (d) carbon dioxide        (CO₂), and (e) a diluent to form a first composition; and    -   2) in a second stage, contacting a polyanionic solid with the        first composition to form a second composition; and    -   3) in a third stage, (a) contacting the second composition with        a polar solvent to release a metal salt of an α,β-unsaturated        carboxylic acid and form a reacted solid; and (b) contacting the        reacted solid with a metal-containing base to produce a        regenerated polyanionic solid.        In this aspect, the first composition can comprise a        metalalactone in which the metalalactone can comprise at least        one ligand. In this aspect, and while not bound by theory, it is        thought that in the second stage, the second composition formed        upon contacting the polyanionic solid with the first composition        can comprise an adduct of a metalalactone and the polyanionic        solid.

This disclosure also provides a continuous process for producing anα,β-unsaturated carboxylic acid or salt thereof, the process comprising

-   -   1) in a first stage, obtaining or providing a first composition        comprising a metalalactone compound and a diluent;    -   2) in a second stage, contacting a polyanionic solid with the        first composition to form a second composition; and    -   3) in a third stage, (a) contacting the second composition with        a polar solvent to release a metal salt of an α,β-unsaturated        carboxylic acid and form a reacted solid; and (b) contacting the        reacted solid with a metal-containing base to produce a        regenerated polyanionic solid.        In this aspect as well, in the second stage, it is thought that        the second composition formed upon contacting the polyanionic        solid with the first composition can comprises an adduct of the        metalalactone and the polyanionic solid.

In the continuous process according to this disclosure, the step ofcontacting the second composition with the polar solvent in the thirdstage to form the reacted solid can be carried out before contacting thereacted solid with the metal-containing base. In an aspect, contactingthe second composition with the polar solvent in the third stage to formthe reacted solid also can be carried out at the same time as contactingthe reacted solid with the metal-containing base.

In the third stage of the continuous process of this disclosure,contacting the second composition with a polar solvent to release ametal salt of an α,β-unsaturated carboxylic acid and form a reactedsolid can be carried out with any polar solvent. At least one polarprotic solvent, at least one polar aprotic solvent, or combinationsthereof can be used to release the metal salt of an α,β-unsaturatedcarboxylic acid. For example, any of the aforementioned diluents thatare polar solvents can be employed. In an aspect, the polar solvent cancomprise or can be selected from water, aliphatic alcohols,acetonitrile, pyridine, aromatic alcohols, ketones, aldehydes, esters,amides, halogenated solvents, ethers, and the like. In a further aspect,any of these aforementioned diluents can be excluded from the polarsolvent or mixture of polar solvents that are used. Therefore, Applicantreserves the right to exclude any of the diluents provided herein.

FIG. 2. illustrates an aspect of this disclosure, showing a conceptualillustration of a continuous process for producing an α,β-unsaturatedcarboxylic acid or salt thereof based upon the reaction process shown inFIG. 1. This FIG. 2 schematic illustrates 1) a first stage in which anickel precursor compound comprising at least one first ligand (Ln-Ni),optionally, at least one second ligand (also generically represented asLn), ethylene, carbon dioxide (CO₂), and toluene (a diluent) arecombined to form a first composition which includes a nickelalactone; 2)a second absorption/elimination stage, in which a polyanionic solid(also termed cocatalyst or activator) is contacted with the firstcomposition to form a second composition, which can include an adduct ofthe nickelalactone and the polyanionic solid; and 3) a third stage inwhich (a) the second composition (typically comprising thenickelalactone-polyanionic solid adduct) is contacted with a polarsolvent to release a metal salt of an α,β-unsaturated carboxylic acidand form a reacted solid, and (b) reacted solid (cocatalyst) iscontacted with a metal-containing base to produce a regeneratedpolyanionic solid. FIG. 2 also illustrates an optional fourth stage inwhich the regenerated polyanionic solid is dried or partially dried.Regarding FIG. 2, this figures is not presented as a complete diagram orschematic of the process with transfer lines, valves and the like beingshown. Rather, FIG. 2 is a conceptual illustration of aspects of theprocess. As an example, the three fixed bed reactors shown in FIG. 2 aresimple illustrations of the three stages and selected portions of thepipes and the like that are specifically related to that stage.

Thus, in an aspect of the continuous process according to thisdisclosure, the second stage and the third stage can be carried out: a)concurrently in a second reactor and a third reactor, respectively; orb) sequentially in a single reactor. In another aspect, the first stage,the second stage, and the third stage are carried out simultaneously ina first reactor, a second reactor, and a third reactor, respectively. Asdemonstrated in the general scheme of FIG. 1, the first stage and firstreactor of the continuous process are generally very different from theother stages and reactors. For example, there is generally a liquidtransfer from the first stage/first reactor to the second stage/secondreactor, because the transition metal complex which can comprise ametalalactone is transferred in a diluent to the second stage/secondreactor, where contact with the polyanionic solid occurs. In principle,the second stage and the third stage of this continuous process can becarried out: a) concurrently in a second reactor and a third reactor,respectively; or alternatively, b) sequentially in a single reactor.Thus, in an aspect, the polyanionic solid is generally insoluble in thediluent.

Moreover, the continuous process according to this disclosure canfurther comprise, in a fourth stage, drying or partially drying theregenerated polyanionic solid. In principle, when the fourth stage ispresent in the continuous process, the second stage, the third stage,and the fourth stage can be carried out: a) concurrently in a secondreactor, a third reactor, and a fourth reactor, respectively; oralternatively, b) sequentially in a single reactor. It is also possibleto carry out, for example, the second stage and the third stage in onereactor, and transfer the resulting material to another reactor to carryout the fourth, drying stage.

With reference to FIG. 1 and FIG. 2, as provided further in thisdisclosure, the continuous process disclosed herein can comprise a stepof contacting a transition metal precursor compound comprising at leastone first ligand, an olefin, and carbon dioxide (CO₂) to form themetalalactone compound. That is, at least one ligand of the transitionmetal precursor compound can be carried over to the metalalactonecompound. In further aspects, the process can further comprise a step ofcontacting a transition metal precursor compound comprising at least onefirst ligand with at least one second ligand, an olefin, and carbondioxide (CO₂) to form the metalalactone compound. In this aspect, theligand set of the metalalactone typically comprises the at least oneligand in addition to the metalalactone moiety. That is, themetalalactone compound can comprise the at least one first ligand, theat least one second ligand, or a combination thereof. In an aspect, forexample, a transition metal precursor compound can be Ni(COD)₂, and onesuitable second ligand can be a diphosphine ligand, and themetalalactone compound can comprise the nickelalactone moiety and thediphosphine ligand.

In some aspects, a first stage includes obtaining or providing a firstcomposition comprising a metalalactone compound and a diluent, and in asecond stage, the a polyanionic solid is contacted with the firstcomposition comprising the metalalactone to form a second composition.These contacting steps can involve contacting, in any order, themetalalactone, the diluent, and the polyanionic solid, and additionalunrecited materials. Likewise, additional materials or features can beemployed in the third stage where the second composition is contactedwith a polar solvent to release a metal salt of an α,β-unsaturatedcarboxylic acid and form a reacted solid, and the reacted solid iscontacting with a metal-containing base to produce a regeneratedpolyanionic solid. Further, it is contemplated that the continuousprocesses for producing an α,β-unsaturated carboxylic acid or a saltthereof by a metalalactone elimination reaction can employ more than onemetalalactone and/or more than one polyanionic solid. Additionally, amixture or combination of two or more diluents can be employed.

According to an aspect, the polyanionic solid used in the continuousprocess can comprise a fixed bed. The polyanionic solid used in thecontinuous process can be formed onto beads or be supported on aninorganic or organic carrier material. Any suitable reactor, vessel, orcontainer can be used in the recited stages, and as described herein, asingle vessel can be used in more than one stage, for example, stage twoand stage three. Non-limiting examples of the polyanionic solid caninclude a flow reactor, a fixed bed reactor, a moving reactor bed, and astirred tank reactor. In particular aspects consistent with thisdisclosure, the metalalactone and the diluent can contact a fixed bed ofthe polyanionic solid, for instance, in a suitable vessel, such as in acontinuous fixed bed reactor. In further aspects, combinations of morethan one polyanionic solid can be used, such as a mixed bed of a firstpolyanionic solid and a second polyanionic solid, or sequential beds ofa first polyanionic solid and a second polyanionic solid. In these andother aspects, the feed stream can flow upward or downward through thefixed bed. For instance, the metalalactone and the diluent can contactthe first polyanionic solid and then the second polyanionic solid in adownward flow orientation, and the reverse in an upward floworientation. In a different aspect, the metalalactone and thepolyanionic solid can be contacted by mixing or stirring in the diluent,for instance, in a suitable vessel, such as a stirred tank reactor.

In an aspect, the continuous process for producing an α,β-unsaturatedcarboxylic acid or a salt thereof can include forming an adduct of themetalalactone and the polyanionic solid and its associated metalcations. Without intending to be bound by theory, there is someinteraction between the metalalactone and the polyanionic solid and itsassociated metal cations that are believed to destabilize themetalalactone for its elimination of the metal acrylate. Thisinteraction can be referred to generally as an adduct of themetalalactone and the polyanionic solid or an adduct of theα,β-unsaturated carboxylic acid with the polyanionic solid. This adductcan contain all or a portion of the α,β-unsaturated carboxylic acid andcan be inclusive of salts of the α,β-unsaturated carboxylic acid.

The continuous process disclosed herein involves applying reactionconditions to a reaction mixture suitable to form an α,β-unsaturatedcarboxylic acid or a salt thereof, for example, subjecting the secondcomposition, which may include an adduct of the metalalactone and thepolyanionic solid, to chemical reagent or reaction conditions ortreatment that produce the α,β-unsaturated carboxylic acid or its salt.Various methods can be used to liberate the α,β-unsaturated carboxylicacid or its salt, from the combination of the second composition. In oneaspect, for instance, this contacting occurs in a third stage, which cancomprise contacting the second composition, which may include an adductof the metalalactone and the polyanionic solid, with an acid.Representative and non-limiting examples of suitable acids can includeHCl, acetic acid, and the like, as well as combinations thereof. Inanother aspect, this stage can comprise contacting the secondcomposition with a base. Representative and non-limiting examples ofsuitable bases can include carbonates (e.g., Na₂CO₃, Cs₂CO₃, MgCO₃),hydroxides (e.g., Mg(OH)₂, Na(OH), alkoxides (e.g., Al(O^(i)Pr)₃,Na(O^(t)Bu), Mg(OEt)₂), and the like, as well as combinations thereof(^(i)Pr=isopropyl, ^(t)Bu=tert-butyl, Et=ethyl). In yet another aspect,the third stage can comprise contacting the second composition with asuitable solvent. Representative and non-limiting examples of suitablesolvents can include carbonyl-containing solvents such as ketones,esters, amides, etc. (e.g., acetone, ethyl acetate,N,N-dimethylformamide, etc., as described herein above), alcoholsolvents, water, and the like, as well as combinations thereof.

In an aspect of the continuous process of this disclosure, thecontacting step of the third stage further comprises heating the secondcomposition to any suitable temperature. That is, the release of theα,β-unsaturated carboxylic acid or its salt can comprise heating theadduct of the metalalactone and the polyanionic solid and its associatedmetal cations to any suitable temperature. This temperature can be in arange, for example, from 50 to 1000° C., from 100 to 800° C., from 150to 600° C., from 250 to 1000° C., from 250° C. to 550° C., or from 150°C. to 500° C. The duration of heating is not limited to any particularperiod of time, as long of the period of time is sufficient to liberatethe α,β-unsaturated carboxylic acid from the polyanionic solid. As thoseof skill in the art recognize, the appropriate treating step dependsupon several factors, such as the particular diluent used in theprocess, and the particular polyanionic solid used in the process,amongst other considerations. One further treatment step can comprise,for example, a workup step with additional olefin to displace analkene-metal bound acrylate.

Illustrative and non-limiting examples of suitable olefins that can beused in the continuous process of this disclosure include, but are notlimited to, ethylene, propylene, butene (e.g., 1-butene), pentene,hexene (e.g., 1-hexene), heptane, octene (e.g., 1-octene), and styreneand the like, as well as combinations thereof. In aspects of thisprocess that utilize ethylene, the step of contacting a transition metalprecursor compound with an olefin and carbon dioxide (CO₂) can beconducted using any suitable pressure of ethylene, or any pressure ofethylene disclosed herein, e.g., from 10 psig (70 KPa) to 1,000 psig(6,895 KPa), from 25 psig (172 KPa) to 500 psig (3,447 KPa), or from 50psig (345 KPa) to 300 psig (2,068 KPa), and the like. Further, theolefin can be ethylene, and the step of contacting a transition metalprecursor compound with an olefin and carbon dioxide (CO₂) can beconducted using a constant addition of the olefin, a constant additionof carbon dioxide, or a constant addition of both the olefin and carbondioxide, to provide the reaction mixture. By way of example, in aprocess wherein the ethylene and carbon dioxide (CO₂) are constantlyadded, the process can utilize an ethylene:CO₂ molar ratio of from 5:1to 1:5, from 3:1 to 1:3, from 2:1 to 1:2, or about 1:1, to provide thereaction mixture.

According to a further aspect of the above process that utilizes atransition metal precursor compound, the process can include the step ofcontacting a transition metal precursor compound with an olefin andcarbon dioxide (CO₂) conducted using any suitable pressure of CO₂, orany pressure of CO₂ disclosed herein, e.g., from 20 psig (138 KPa) to2,000 psig (13,790 KPa), from 50 psig (345 KPa) to 750 psig (5,171 KPa),or from 100 psig (689 KPa) to 300 psig (2,068 KPa), and the like. In anyof the processes disclosed herein, the processes can further comprise astep of monitoring the concentration of at least one reaction mixturecomponent, at least one elimination reaction product, or a combinationthereof, for any reason, such as to adjust process parameters in realtime, to determine extent or reaction, or to stop the reaction at thedesired point.

As illustrated, this process that utilizes a transition metal precursorcompound comprising at least one first ligand includes one aspect inwhich no second ligand is employed in the contacting step, and anotheraspect in which a second ligand is used in the contacting step. That is,one aspect involves the contacting step of the process comprisingcontacting the transition metal precursor compound comprising at leastone first ligand with the at least one second ligand. The order ofcontacting can be varied. For example, the contacting step of theprocess disclosed above can comprise contacting (a) the transition metalprecursor compound comprising at least one first ligand with (b) the atleast one second ligand to form a pre-contacted mixture, followed bycontacting the pre-contacted mixture with the remaining components(c)-(f) in any order to provide the reaction mixture.

In further aspects related to the stages of the continuous process, thecontacting step of the first stage which uses a transition metalprecursor can further comprise contacting the transition metal precursorcompound comprising at least one first ligand with the at least onesecond ligand, that is, at least one second ligand is employed. In anaspect, the contacting step of the first stage can comprise contacting(a) the transition metal precursor compound with (b) the at least onesecond ligand to form a pre-contacted mixture, followed by contactingthe pre-contacted mixture with (c) the olefin, (d) carbon dioxide (CO₂),and (e) the diluent to form the first composition. Moreover, thecontacting step of the first stage can comprise contacting thecomponents (a)-(e) in any order.

In the continuous process of this disclosure, the contacting step of thesecond stage can comprise contacting the polyanionic solid with a seconddiluent to form a mixture, followed by contacting the mixture with thefirst composition to form the second composition.

In an aspect of the continuous process, the contacting step in the thirdstage can further comprise contacting an additive selected from an acid,a base, or a reductant. For example, the contacting step of the thirdstage further comprises contacting the second composition with anysuitable acid, or any acid disclosed herein, e.g., HCl, acetic acid, andthe like. In an aspect, the contacting step of the third stage mayfurther comprise contacting the second composition with any suitablesolvent, or any solvent disclosed herein, e.g., carbonyl-containingsolvents such as ketones, esters, amides, etc. (e.g., acetone, ethylacetate, N,N-dimethylformamide), alcohols, water, and the like.

The continuous process according to this disclosure can further comprisea step of isolating the α,β-unsaturated carboxylic acid, or the saltthereof, e.g., using any suitable separation/purification procedure orany separation/purification procedure disclosed herein, e.g.,evaporation, distillation, chromatography, and the like.

As above, any suitable reactor, vessel, or container can be used tocontact the transition metal-ligand, olefin, diluent, polyanionic solid,and carbon dioxide, whether using a fixed bed of the polyanionic solid,a stirred tank for contacting (or mixing), or some other reactorconfiguration and process. While not wishing to be bound by thefollowing theory, a proposed and illustrative reaction scheme for thisprocess is provided below.

Independently, the contacting and forming steps of any of the processesdisclosed herein (i.e., for performing a metalalactone eliminationreaction, for producing an α,β-unsaturated carboxylic acid, or a saltthereof), can be conducted at a variety of temperatures, pressures, andtime periods. For instance, the temperature at which the components instep (1) are initially contacted can be the same as, or different from,the temperature at which the forming step (2) is performed. As anillustrative example, in the contacting step, the components can becontacted initially at temperature T₁ and, after this initial combining,the temperature can be increased to a temperature T₂ for the formingstep (e.g., to form the α,β-unsaturated carboxylic acid, or the saltthereof). Likewise, the pressure can be different in the contacting stepand the forming step. Often, the time period in the contacting step canbe referred to as the contact time, while the time period in formingstep can be referred to as the reaction time. The contact time and thereaction time can be, and often are, different.

In an aspect, the contacting step and/or the forming step of theprocesses disclosed herein, that is, the contacting step in any one ormore of the first stage, the second stage, and/or the third stage, canbe conducted at a temperature in a range from 0° C. to 250° C.;alternatively, from 20° C. to 200° C.; alternatively, from 0° C. to 95°C.; alternatively, from 10° C. to 75° C.; alternatively, from 10° C. to50° C.; or alternatively, from 15° C. to 70° C. In these and otheraspects, after the initial contacting, the temperature can be changed,if desired, to another temperature for the forming step. Thesetemperature ranges also are meant to encompass circumstances where thecontacting step and/or the forming step can be conducted at a series ofdifferent temperatures, instead of at a single fixed temperature,falling within the respective ranges.

In an aspect, the contacting step and/or the forming step of theprocesses disclosed herein, for example, the contacting step in any oneor more of the first stage, the second stage, and/or the third stage,can be conducted at a pressure in a range from 5 (34 KPa) to 10,000 psig(68,948 KPa), such as, for example, from 5 psig (34 KPa) to 2500 psig(17,237 KPa). In some aspects, the pressure can be in a range from 5psig (34 KPa) to 500 psig (3,447 KPa); alternatively, from 25 psig (172KPa) to 3000 psig (20,684 KPa); alternatively, from 45 psig (310 KPa) to1000 psig (6,895 KPa); or alternatively, from 50 psig (345 KPa) to 250psig (1,724 KPa).

The contacting step of the processes is not limited to any particularduration of time. That is, the respective components can be initiallycontacted rapidly, or over a longer period of time, before commencingthe forming step. Hence, the contacting step can be conducted, forexample, in a time period ranging from as little as 1-30 seconds to aslong as 1-12 hours, or more. In non-continuous or batch operations, theappropriate reaction time for the forming step can depend upon, forexample, the reaction temperature, the reaction pressure, and the ratiosof the respective components in the contacting step, among othervariables. Generally, however, the forming step can occur over a timeperiod that can be in a range from 1 minute to 96 hours, such as, forexample, from 2 minutes to 96 hours, from 5 minutes to 72 hours, from 10minutes to 72 hours, or from 15 minutes to 48 hours.

In the continuous process, the contacting step in any one or more of thesecond stage and/or the third stage can be conducted at any suitableweight hourly space velocity (WHSV) or any WHSV disclosed herein, e.g.,from 0.05 to 50 hr⁻¹, from 1 to 25 hr⁻¹, from 1 to 5 hr⁻¹, etc., basedon the amount of the polyanionic solid. Thus, the continuous process canbe expressed in terms of weight hourly space velocity (WHSV)—the ratioof the weight of the metalalactone (or transition metal-ligand complex,or the total of the reaction solution containing the transition metalprecursors, first ligands, second ligands, olefin, diluent, anionicpolyelectrolyte, and carbon dioxide metal-ligand complex) which comes incontact with a given weight of anionic electrolyte per unit time (forexample, hr⁻¹). While not limited thereto, the WHSV employed, based onthe amount of the polyanionic solid, can be in a range from 0.05 to 100hr⁻¹, from 0.05 to 50 hr⁻¹, from 0.075 to 50 hr⁻¹, from 0.1 to 25 hr⁻¹,from 0.5 to 10 hr⁻¹, from 1 to 25 hr⁻¹, or from 1 to 5 hr⁻¹.

In the processes disclosed herein, the molar yield of theα,β-unsaturated carboxylic acid, or the salt thereof), based on themetalalactone (or the transition metal-ligand complex) is at least 2%,and more often can be at least 5%, at least 10%, or at least 15%. Inparticular aspects of this disclosure, the molar yield can be at least18%, at least 20%, at least 25%, at least 35%, at least 50%, at least60%, at least 75%, or at least 85%, or at least 90%, or at least 95%, orat least 100%. That is, catalytic formation of the α,β-unsaturatedcarboxylic acid or the salt thereof can be effected with the disclosedsystem. For example, the molar yield of the α,β-unsaturated carboxylicacid, or the salt thereof, based on the metalalactone or based on thetransition metal precursor compound can be at least 20%, at least 40%,at least 60%, at least 80%, at least 100%, at least 120%, at least 140%,at least 160%, at least 180%, at least 200%, at least 250%, at least300%, at least 350%, at least 400%, at least 450%, or at least 500%.

The specific α,β-unsaturated carboxylic acid (or salt thereof) that canbe formed or produced using the processes of this disclosure is notparticularly limited. Illustrative and non-limiting examples of theα,β-unsaturated carboxylic acid can include acrylic acid, methacrylicacid, 2-ethylacrylic acid, cinnamic acid, and the like, as well ascombinations thereof. Illustrative and non-limiting examples of the saltof the α,β-unsaturated carboxylic acid can include sodium acrylate,potassium acrylate, lithium acrylate, magnesium acrylate, sodium(meth)acrylate, and the like, as well as combinations thereof.

Once formed, the α,β-unsaturated carboxylic acid (or salt thereof) canbe purified and/or isolated and/or separated using suitable techniqueswhich can include, but are not limited to, evaporation, distillation,chromatography, crystallization, extraction, washing, decanting,filtering, drying, and the like, including combinations of more than oneof these techniques. In an aspect, the process can for performing ametalalactone elimination reaction (or the process for producing anα,β-unsaturated carboxylic acid, or a salt thereof) can further comprisea step of separating or isolating the α,β-unsaturated carboxylic acid(or salt thereof) from other components, e.g., the diluent, the anionicelectrolyte, and the like.

EXAMPLES

The invention is further illustrated by the following examples, whichare not to be construed in any way as imposing limitations to the scopeof this invention. Various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, cansuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

General Considerations

Unless otherwise noted, all operations were performed under purifiednitrogen or vacuum using standard Schlenk or glovebox techniques.Toluene (Honeywell) and tetrahydrofuran (Aldrich) was degassed and driedover activated 4 Å molecular sieves under nitrogen. Sodiumtert-butoxide, potassium tert-butoxide, poly(4-vinylphenol)(M_(w)˜11,000 g/mol), poly(4-vinylphenol-co-methyl(meth)acrylate)(M_(w)˜8,000-12,000 g/mol), and brominated poly(4-vinylphenol)(M_(w)˜5,800 g/mol) were purchased from Sigma-Aldrich and used asreceived. Phenol/formaldehyde resin was purchased as hollow beads(˜5-127 μm) from Polysciences, Inc. Bis(1,5-cyclooctadiene)nickel(0) and1,2-Bis(dicyclohexylphosphino)ethane were purchased from Strem and wereused as received. (TMEDA)Ni(CH₂CH₂CO₂) was prepared according toliterature procedures (Fischer, R; Nestler, B., and Schutz, H. Z. anorg.allg. Chem. 577 (1989) 111-114).

Preparation of Compounds Sodium poly(4-vinylphenol)

To sodium tert-butoxide (15 g, 125 mmol) and poly(4-vinylphenol) (12 g,125 mmol) was added toluene (600 mL) in a 1 L round-bottomed flaskequipped with a stirbar. The mixture was stirred for four days then fritfiltered. The filter cake was washed with 30 mL of toluene followed by15 mL of toluene, then allowed to dry. The dry cake was washed with 3×20mL of toluene leaving a solid.

Potassium poly(4-vinylphenol)

Prepared analogously to sodium poly(4-vinylphenol) substitutingpotassium tert-butoxide for sodium tert-butoxide.

Sodium poly(4-vinylphenol-co-methyl(meth)acrylate)

Prepared analogously to sodium poly(4-vinylphenol) substitutingpoly(4-vinylphenol-co-methyl(meth)acrylate) for poly(4-vinylphenol).

Sodium poly(4-vinylphenol), Brominated

Prepared analogously to sodium poly(4-vinylphenol) substitutingpoly(4-vinylphenol), brominated for poly(4-vinylphenol).

Sodium Phenol/Formaldehyde Resin

Phenolic resin (phenol/formaldehyde resin) was suspended in a solutionof sodium hydroxide in either water or methanol and stirred at 55° C.overnight prior to filtration, and subsequently washed with copiousamounts of the solvent in which it was treated. The solid was then driedunder vacuum prior to storage under nitrogen.

Examples 1-10 Experimental Procedure for Ethylene/Carbon DioxideCoupling

The ethylene/carbon dioxide reaction of these examples is set out inreaction (1) below, and specific reagents, reaction conditions, andyields are set out in Table 1.

A 1-liter autoclave pressure reactor was charged with solvent followedby a combined mixture of Ni(COD)₂ (0.10 mmol),bis(dicyclohexylphosphino)ethane (0.11 mmol), and poly(4-vinylphenoxide)(1.00 g) in 10 mL of solvent. The reactor was set to 50° C., pressurizedwith ethylene at the desired level, and equilibrated for 5-10 minutes(min) prior to being pressurized and equilibrated with carbon dioxide.The reactor was then set to 100° C. and stirred for 6 hours. After thisreaction time, and after cooling to ambient temperature, the reactor wasslowly vented and the mixture was collected. The solvent was removed invacuo and the residue was stirred in 10-20 mL of deuterium oxide for 30min prior to the addition of a sorbic acid/acetone-d₆ solution. Themixture was filtered and analyzed by NMR (sorbic acid is used as theinternal standard) for acrylate yield determination.

TABLE 1 Ethylene/carbon dioxide coupling and acrylate yields [Sol-Acrylate vent] [C₂H₄] [CO₂] Yield Example M Solvent (mL) (psi (KPa))(psi (KPa) (%) 1 Na Toluene 300 150 100 14 (1,034)   (689) 2 K Toluene300 100 150 68 (689) (1,034)   3 K Toluene 300 150 300 117 (1,034)  (2,068)   4 K Toluene 50 150 300 42 (1,034)   (2,068)   5 K Toluene 50 75 300 25 (517) (2,068)   6 Na Toluene 300 150 300 104 (1,034)  (2,068)   7 Na^(A) Toluene 300 150 300 130 (1,034)   (2,068)   8 NaToluene 50 150 300 23 (1,034)   (2,068)   9 Na THF 50 150 300 52(1,034)   (2,068)   10 Na THF 300 150 300 62 (1,034)   (2,068)  ^(A)2.00 g of poly(4-vinylphenoxide) were used in this example.

Examples 11-17 Experimental Procedure for Nickelalactone Conversion toAcrylate

To study the elimination step of the disclosed process, the efficienciesof various alkoxides or aryloxides for the conversion of adiphosphine-stabilized nickelalactone to acrylic acid were assessed.Specifically, the following experiments show the efficiencies of sodiumand potassium (4-vinylphenoxide) for the conversion of an in situprepared diphosphine-stabilized nickelalactone, and the data werecompared to the conversion using molecular sodium tert-butoxide foracrylate formation from the analogous nickelalactones. The metalalactoneto acrylate conversion reaction of these examples is set out in reaction(2) below, and specific reagents, reaction conditions, and yields areset out in Table 2. In reaction (2), the “metal alkoxide” includes thepolymeric alkoxides shown in Table 2.

In a 10 mL vial, (TMEDA)Ni(CH₂CH₂CO₂) (0.018 mmol),bis(dicyclohexylphosphino)-ethane (0.018 mmol), poly(4-vinylphenoxide),and solvent (5 mL) were combined and stirred at 60° C. for 30-60 min.Following removal of solvent, the solid residue was taken up in D₂O (3-5mL) for 30 min and filtered. An aliquot of a prepared sorbicacid/acetone-d₆ solution was added for determination of acrylic acidyield by NMR.

TABLE 2 Nickelalactone conversion to acrylate and acrylate yields Exam-[Metal Alkoxide] % ple Metal Alkoxide Solvent (mg) Yield 11 Sodiumpoly(4- Toluene 100 33 vinylphenoxide) 12 Sodium poly(4- Toluene 250 32vinylphenoxide) 13 Sodium poly(4- Toluene 25 15 vinylphenoxide) 14Potassium poly(4- Toluene 100 24 vinylphenoxide) 15 Sodium poly(4-Toluene 100 66 vinylphenol-co- methyl(meth)acrylate) 16 Sodium poly(4-Toluene 100 6 vinylphenol), brominated 17 Sodium tert-butoxide THF 7 16

The study from Table 2 reveals, among other things, that increasing thesodium poly(4-vinylphenoxide) amount from 100 mg to 250 mg (Examples 11and 12) provides the same overall yield of the sodium acrylate/acrylicacid. Using the potassium salt (Example 14) as compared to the sodiumsalt (Example 11) of the poly(4-vinylphenoxide) somewhat lowered theyield of the sodium acrylate/acrylic acid.

Accordingly, this disclosure demonstrates at least the following: 1) afacile acid-base reaction that affords a metal polyvinylphenoxide orvariants thereof in excellent yields with negligible byproducts; 2) anickelalactone destabilization and cleavage that can proceed insurprisingly short time frames, that is, shorter times than expected (<1hour); and 3) the increased loadings of metal polyvinylphenoxide doesnot diminish the resulting yield of the acrylate/acrylic acid.

Example 18 Polymeric Stationary Phases for Catalytic Acrylate Formation

The present disclosure also provides for using polymeric stationaryphases, such as polyphenol resins (e.g. poly(4-vinylphenolate) resins)or polyaromatic resins (e.g. phenol-formaldehyde resins) in a column orother suitable solid state configuration, in which formation of theacrylate from a metalalactone (such as a nickelalactone) in a mobilephase can be effected.

FIG. 1 illustrates one way in which a polymeric stationary phasecatalyst column can be configured, in which the coupling reaction andelution of the metal acrylate from the column can be carried out. Asshown, a metal (e.g. sodium) poly(4-vinylphenolate) resins were found tobe suitable polyanionic solid promoters or “co-catalysts” in theconversion of olefin/carbon dioxide-derived nickelalactoneintermediates. This method can provide both easier separation ofacrylate from other materials and ease of regeneration of the polymericsupport materials to its salt form, such as sodiumpoly(4-vinylphenoxide).

Example 19-21 Sodium-Treated Crosslinked Polyaromatic Resins asStoichiometric Co-Catalysts in Olefin/Carbon Dioxide Conversion toα,β-Unsaturated Carboxylates

Because the metal (e.g. sodium) poly(4-vinylphenolate) resins were foundto be suitable promoters and sources of cations in the conversion ofolefin and carbon dioxide-derived nickelalactone intermediates, anevaluation of their crosslinked analogues was undertaken. It wasbelieved that these crosslinked polyaromatic resins would besufficiently insoluble in many commercial diluents to be applicabilityas a polymeric promoters and cation sources in a fixed bed/columnreactor setting. This method further allows for the potentialregeneration of the spent solid co-catalyst in both aqueous (forexample, sodium hydroxide in water) and/or organic media (for example,sodium alkoxide in toluene).

The following reaction (3) illustrates the conversion reaction of anolefin and carbon dioxide-derived nickelalactone intermediate that wasundertaken to evaluate some crosslinked polyelectrolyte analogues.Reaction conditions for reaction (3) are: 0.10 mmol [Ni], 0.11 mmoldiphosphine ligand, 500 mL of toluene, 1.0 g of sodium-treated,crosslinked polyaromatic resin (solid activator). The reactor wasequilibrated to 150 psi of ethylene followed by 300 psi of carbondioxide prior to heating. The yield reported in Table 3 was determinedby ¹H NMR spectroscopy in a D₂O/(CD₃)₂CO mixture relative to a sorbicacid standard.

The following table describe various examples where commercialpolyaromatic resins, which were either further treated with a sodiumbase under appropriate conditions or are commercially available in thesodium form, were found to be effective in the nickel-mediated synthesisof sodium acrylate from ethylene and carbon dioxide.

TABLE 3 Nickel-mediated conversion of carbon dioxide and ethylene tosodium acrylate with sodium treated polyaromatics.^(A) Base & [Solid]:Acrylate Exam- Co-catalyst Sodium [Na] yield ple Solvent Solid Source(wt) (%) 19 toluene Phenol/ NaOH 0.3 1.8 Formaldehyde (MeOH) 20 toluenePhenol/ NaOH 0.3 6.0 Formaldehyde (aq) 21 toluene Phenol/ NaO—t-Bu 1.0n.d.^(B) Formaldehyde ^(A)Reaction Conditions: 0.10 mmol [Ni], 0.11 mmoldiphosphine ligand, 500 mL toluene, 1.0 g solid activator(phenol-formaldehyde resin). Reactor was equilibrated to 150 psiethylene followed by 300 psi carbon dioxide prior to heating. Yielddetermined by¹H NMR spectroscopy in D₂O/(CD₃)₂CO mixture relative tosorbic acid standard. ^(B)None detected.

Even though the yields of acrylate when employing these sodium-treatedcrosslinked resins may be modest, the data indicate that thenickel-mediated conversion of carbon dioxide and ethylene to sodiumacrylate with sodium treated crosslinked polyaromatic resins can becarried out. Further, the insolubilities of these resins in manycommercial solvents will allow for their utility in fixed bed/columnconfigurations.

The phenol/formaldehyde resins can be treated with sodium hydroxide toproduce what are believed to be sodium aryloxide sites that are activefor promoting nickelalactone scission, and more so when the NaOH isdissolved in water to provide a higher solubility (Example 20) versusmethanol (Example 19).

Example 21 Crosslinked Polyaromatic Resin Co-Catalysts in Olefin/CarbonDioxide Conversion to α,β-Unsaturated Carboxylates, Using Co-Monomers

In this example, co-monomer phenol compounds are used together withformaldehyde to prepare the crosslinked polyaromatic resins for use asdescribed according to the disclosure. The resin was prepared using theco-monomer combination of resorcinol (m-dihydroxybenzene) and2-fluorophenol monomer with formaldehyde, and the resulting resin wassodium-treated (NaOH, dissolved in water or alcohol) to generate thepolyanionic solid, according to equation (4).

The polyaromatic resin is thought to act as a co-catalyst upon treatmentwith sodium hydroxide because of what are believed to be sodiumaryloxide sites that promote nickelalactone scission. It is noted thatincreased crosslink density is obtained using longer drying times toremove trapped excess water.

Examples 22-25 Additional Stationary Phases for Catalytic AcrylateFormation

The present disclosure also provides for using other polymericstationary phases and modifications thereof, for example, in a column orother suitable solid state configuration. Further variations of thistechnology include but are not limited to the following examples.

Example 22

Polymer modifications that include acid-base reaction being effectedusing a wide range of metal bases, including alkali and alkalinehydroxides, alkoxides, aryloxides, amides, alkyl or aryl amides, and thelike, such that an assortment of electrophiles can be used innickelalactone destabilization as demonstrated herein for thepolyvinylphenols.

Example 23

Polymer modifications can also include using variants of thepolyvinylphenol, that can be prepared by polymerization ofhydroxyl-substituted styrenes having a variety of organic and inorganicsubstituents, such as alkyls, halogens, and heteroatom substituents.

Example 24

Polymer modifications can also include using co-polymers based on, forexample, the co-polymerization of a protected hydroxyl-substitutedstyrene (such as acetoxystyrene) with other styrenes and (meth)acrylates(typically followed by hydrolysis to generate the polyvinylphenolco-polymer) to produce libraries of polymeric electrophiles.

Example 25

Polymer support variations are also envisioned, including for examplepolymers that can be supported onto beads or other surfaces. One classof polymer support variation that is envisioned is a cast polymer thatcan function as an ion exchange membrane.

Example 26-29 Chemically-Treated Solid Oxides as Co-Catalysts inOlefin/Carbon Dioxide Conversion to α,β-Unsaturated Carboxylates

The following examples demonstrate the utility of the chemically-treatedsolid oxides as co-catalyst for the olefin-CO₂ coupling reactions inacrylate formation. The chemically-treated solid oxides tested weresulfated alumina and fluorided silica-coated alumina.

When the polyanionic solid is a chemically treated solid oxide,preparing the chemically treated solid oxide initially involvescalcining the chemically treated solid oxide to eliminate or greatlyreduce water and to introduce the electron withdrawing anion, in thiscase, fluoride. However, the continuous process involve a regenerationof the polyanionic solids which can be effected by base treatment asdescribed herein. The continuous process also involves a stage in whichthe second composition comprising the combination of the metal complex(such as metalalactone) and the polyanionic solid (such as a chemicallytreated solid oxide) are contacted with a polar solvent such as water torinse and/or release a metal salt of an α,β-unsaturated carboxylic acidand form a reacted solid. Subsequent regeneration of the polyanionicsolids is generally effected by base treatment, and a subsequent waterwash can be used.

Therefore, the water reaction and subsequent regeneration of thepolyanionic solid suggested that the regenerated co-catalyst solid maynot be moisture-free. The following tests were conducted with thefluorided silica-coated alumina and sulfated alumina, including tests inwhich the fluorided silica-coated alumina and sulfated alumina werewashed with water followed by treatment with sodium tert-butoxide, tore-generate the co-catalyst. These solids were screened for acrylateconversion efficacy versus their non-water washed analogs. The non-waterwashed analogs were completely water-free from calcination as well asbase treatment in dry solvent. These examples are set out in thefollowing reaction and the results are provided in the following table.

TABLE 4 Nickel-mediated conversion of carbon dioxide and ethylene tosodium acrylate with chemically treated solid oxides (SSAs).^(A) Exam-SSA Acrylate yield ple Co-catalyst Solvent (%) 26 NaO—t-Bu treatedsulfated Toluene 102 alumina 27 NaO—t-Bu treated fluorided Toluene 131silica-coated alumina 28 Sulfated alumina treated Toluene 350 with waterfollowed by NaO—t-Bu 29 Fluorided silica-coated Toluene 218 aluminatreated by water followed by NaO—t-Bu ^(A)Reaction Conditions: 0.10 mmol[Ni], 0.11 mmol diphosphine ligand, 500 mL solvent, 1.0 g SSA solidactivator. Reactor was equilibrated to 150 psi ethylene followed by 300psi carbon dioxide prior to heating. Extracted in to D₂O for yielddetermined by ¹H NMR spectroscopy relative to sorbic acid standard.

The water-washed co-catalysts (Examples 28-29) were observed to producesubstantially more acrylate than their non-water-washed analogs(Examples 26-27). These results were surprising because it wasunexpected that aqueous regeneration would still support the activity ofthe co-catalyst, and especially surprising that the acrylate productionwas substantially better than the non-aqueous and dry co-catalystexamples.

The invention is described above with reference to numerous aspects andembodiments, and specific examples. Many variations will suggestthemselves to those skilled in the art in light of the above detaileddescription. All such obvious variations are within the full intendedscope of the appended claims. Other aspects of the invention caninclude, but are not limited to, the following Aspects. Many aspects aredescribed as “comprising” certain components or steps, butalternatively, can “consist essentially of” or “consist of” thosecomponents or steps unless specifically stated otherwise.

Aspect 1. A continuous process for producing an α,β-unsaturatedcarboxylic acid or salt thereof, the process comprising

-   -   1) in a first stage, contacting (a) a transition metal precursor        compound comprising at least one first ligand, (b) optionally,        at least one second ligand, (c) an olefin, (d) carbon dioxide        (CO₂), and (e) a diluent to form a first composition; and    -   2) in a second stage, contacting a polyanionic solid with the        first composition to form a second composition; and    -   3) in a third stage, (a) contacting the second composition with        a polar solvent to release a metal salt of an α,β-unsaturated        carboxylic acid and form a reacted solid; and (b) contacting the        reacted solid with a metal-containing base to produce a        regenerated polyanionic solid.

Aspect 2. A continuous process for producing an α,β-unsaturatedcarboxylic acid or salt thereof, the process comprising

-   -   1) in a first stage, contacting (a) a transition metal precursor        compound comprising at least one first ligand, (b) optionally,        at least one second ligand, (c) an olefin, (d) carbon dioxide        (CO₂), and (e) a diluent to form a first composition comprising        a metalalactone compound; and    -   2) in a second stage, contacting a polyanionic solid with the        first composition to form a second composition; and    -   3) in a third stage, (a) contacting the second composition with        a polar solvent to release a metal salt of an α,β-unsaturated        carboxylic acid and form a reacted solid; and (b) contacting the        reacted solid with a metal-containing base to produce a        regenerated polyanionic solid.

Aspect 3. A continuous process for producing an α,β-unsaturatedcarboxylic acid or salt thereof, the process comprising

-   -   1) in a first stage, obtaining or providing a first composition        comprising a metalalactone compound and a diluent;    -   2) in a second stage, contacting a polyanionic solid with the        first composition to form a second composition; and    -   3) in a third stage, (a) contacting the second composition with        a polar solvent to release a metal salt of an α,β-unsaturated        carboxylic acid and form a reacted solid; and (b) contacting the        reacted solid with a metal-containing base to produce a        regenerated polyanionic solid.

Aspect 4. A continuous process for producing an α,β-unsaturatedcarboxylic acid or salt thereof, the process comprising

-   -   1) in a first stage, obtaining or providing a first composition        comprising a metalalactone compound and a diluent;    -   2) in a second stage, contacting a polyanionic solid with the        first composition to form a second composition comprising an        adduct of the metalalactone compound and the polyanionic solid;        and    -   3) in a third stage, (a) contacting the second composition with        a polar solvent to release a metal salt of an α,β-unsaturated        carboxylic acid and form a reacted solid; and (b) contacting the        reacted solid with a metal-containing base to produce a        regenerated polyanionic solid.

Aspect 5. A continuous process according to any one of Aspects 1-4,wherein contacting the second composition with the polar solvent in thethird stage to form the reacted solid is carried out before contactingthe reacted solid with the metal-containing base.

Aspect 6. A continuous process according to any one of Aspects 1-4,wherein contacting the second composition with the polar solvent in thethird stage to form the reacted solid is carried out at the same time ascontacting the reacted solid with the metal-containing base.

Aspect 7. A continuous process according to any one of Aspects 1-4,wherein the polar solvent comprises water, an aliphatic alcohol, anaromatic alcohol, an inorganic acid, an organic acid, or a combinationthereof.

Aspect 8. A continuous process according to any one of Aspects 1-6,wherein:

the first stage and the second stage are carried out: a) concurrently ina first reactor and a second reactor, respectively; or b) sequentiallyin a single reactor; or

the second stage and the third stage are carried out: a) concurrently ina second reactor and a third reactor, respectively; or b) sequentiallyin a single reactor.

Aspect 9. A continuous process according to any one of Aspects 1-6,wherein the first stage, the second stage, and the third stage arecarried out simultaneously in a first reactor, a second reactor, and athird reactor, respectively.

Aspect 10. A continuous process according to any one of Aspects 1-6,further comprising, in a fourth stage, drying or partially drying theregenerated polyanionic solid.

Aspect 11. A continuous process according to Aspect 10, wherein thesecond stage, the third stage, and the fourth stage are carried out: a)concurrently in a second reactor, a third reactor, and a fourth reactor,respectively; or b) sequentially in a single reactor.

Aspect 12. The process according to any of the preceding Aspects,wherein the polyanionic solid is insoluble in the diluent.

Aspect 13. The process according to Aspect 2, wherein the secondcomposition comprises an adduct of the metalalactone compound and thepolyanionic solid.

Aspect 14. A continuous process according to any one of Aspects 1-13,wherein the polyanionic solid comprises an alkoxide, an aryloxide, anacrylate, a (meth)acrylate, a sulfonate, an alkyl thiolate, an arylthiolate, an alkyl amide, or an aryl amine group.

Aspect 15. A continuous process according to any one of Aspects 1-13,wherein the polyanionic solid comprises a poly(vinyl aryloxide), apoly(vinyl alkoxide), a poly(acrylate), a poly((meth)acrylate), apoly(styrene sulfonate), a phenol-formaldehyde resin, apolyhydroxyarene-formaldehyde resin (such as a resorcinol-formaldehyderesin), a polyhydroxyarene- and fluorophenol-formaldehyde resin (such asa resorcinol- and 2-fluorophenol-formaldehyde resin), a poly(vinylarylamide), a poly(vinyl alkylamide), or combinations thereof.

Aspect 16. A continuous process according to any one of Aspects 1-13,wherein the polyanionic solid comprises a poly(vinyl aryloxide), apoly(vinyl alkoxide), a substituted analog thereof, or a combinationthereof.

Aspect 17. A continuous process according to any one of Aspects 1-13,wherein the polyanionic solid comprises sodium(poly-4-vinylphenoxide).

Aspect 18. A continuous process according to any one of Aspects 1-13,wherein the polyanionic solid comprises a phenol-formaldehyde resin, apolyhydroxyarene-formaldehyde resin (such as a resorcinol-formaldehyderesin), a polyhydroxyarene- and fluorophenol-formaldehyde resin (such asa resorcinol- and 2-fluorophenol-formaldehyde resin), or combinationsthereof.

Aspect 19. A continuous process according to any one of Aspects 1-13,wherein the polyanionic solid comprises a phenol-formaldehyde resin, aresorcinol-formaldehyde resin, a resorcinol- andfluorophenol-formaldehyde resin, or combinations thereof.

Aspect 20. A continuous process according to any one of Aspects 1-13,wherein the polyanionic solid comprises a phenol-formaldehyde resin or aresorcinol- and 2-fluorophenol-formaldehyde resin.

Aspect 21. A continuous process according to any one of Aspects 1-13,wherein the polyanionic solid comprises a phenol-formaldehyde resin.

Aspect 22. A continuous process according to any one of Aspects 1-21,wherein the polyanionic solid comprises any suitable metal cation, anymetal cation disclosed herein, any suitable Lewis acidic metal cation,or any Lewis acidic metal cation disclosed herein.

Aspect 23. A continuous process according to any one of Aspects 1-21,wherein the polyanionic solid comprises associated metal cationscomprising or selected from an alkali metal, an alkaline earth metal, ora combination thereof.

Aspect 24. A continuous process according to any one of Aspects 1-21,wherein the polyanionic solid comprises associated metal cationscomprising or selected from lithium, sodium, potassium, magnesium,calcium, strontium, barium, aluminum, or zinc.

Aspect 25. A continuous process according to any one of Aspects 1-21,wherein the polyanionic solid comprises associated metal cationscomprising or selected from sodium or potassium.

Aspect 26. A continuous process according to any one of Aspects 1-13,wherein the polyanionic solid comprises a metal oxide.

Aspect 27. A continuous process according to any one of Aspects 1-13,wherein the polyanionic solid comprises a calcined metal oxide.

Aspect 28. A continuous process according to any one of Aspects 26-27,wherein the metal oxide comprises silica, alumina, silica-alumina,silica-coated alumina, aluminum phosphate, aluminophosphate,heteropolytungstate, mullite, titania, zirconia, magnesia, boria, zincoxide, silica-titania, silica-zirconia, a mixed oxide thereof, or anymixture thereof.

Aspect 29. A continuous process according to any one of Aspects 1-13,wherein the polyanionic solid comprises a metal-treated sodium oxide.

Aspect 30. A continuous process according to any one of Aspects 1-13,wherein the polyanionic solid comprises a solid oxide that has beencontacted with the metal-containing base.

Aspect 31. A continuous process according to any one of Aspects 1-13,wherein the polyanionic solid comprises a chemically-treated solid oxidethat has been hydroxylated and subsequently contacted with themetal-containing base.

Aspect 32. A continuous process according to any one of Aspects 1-13,wherein the polyanionic solid comprises, consists of, consistsessentially of, or is selected from a chemically-treated solid oxidecomprising at least one solid oxide that has been treated with at leastone electron withdrawing anion.

Aspect 33. A continuous process according to any one of Aspects 1-13,wherein the polyanionic solid comprises, consists of, consistsessentially of, or is selected from a chemically-treated solid oxide,comprising:

at least one of silica, alumina, silica-alumina, silica-coated alumina,aluminum phosphate, aluminophosphate, heteropolytungstate, mullite,titania, zirconia, magnesia, boria, zinc oxide, silica-titania,silica-zirconia, a mixed oxide thereof, or any mixture thereof, that hasbeen chemically treated with at least one electron withdrawing anion.

Aspect 34. A continuous process according to any one of Aspects 1-13,wherein the polyanionic solid comprises, consists of, consistsessentially of, or is selected from a chemically-treated solid oxide,comprising:

at least one of silica, alumina, silica-alumina, silica-coated alumina,aluminum phosphate, aluminophosphate, heteropolytungstate, mullite,titania, zirconia, magnesia, boria, zinc oxide, silica-titania,silica-zirconia, a mixed oxide thereof, or any mixture thereof, that hasbeen chemically treated with at least one electron withdrawing anion;

wherein the at least one electron withdrawing anion comprises fluoride,chloride, bromide, iodide, phosphate, triflate, trifluoroacetate,sulfate, bisulfate, fluorosulfate, fluoroborate, fluorophosphate,fluorozirconate, fluorotitanate, phosphotungstate, or any combinationthereof.

Aspect 35. A continuous process according to any one of Aspects 32-34,wherein the chemically-treated solid oxide comprises at least onesilica-coated alumina treated with at least one electron-withdrawinganion, wherein: the at least one silica-coated alumina has a weightratio of alumina to silica in a range from about 1:1 to about 100:1, andthe at least one electron-withdrawing anion comprises fluoride,chloride, bromide, phosphate, triflate, bisulfate, sulfate, or anycombination thereof.

Aspect 36. A continuous process according to any one of Aspects 32-34,wherein the chemically-treated solid oxide comprises, consists of,consists essentially of, or is selected from fluorided alumina,chlorided alumina, bromided alumina, fluorided-chlorided alumina,sulfated alumina, fluorided silica-alumina, chlorided silica-alumina,bromided silica-alumina, fluorided-chlorided silica-alumina, sulfatedsilica-alumina, fluorided silica-titania, chlorided silica-titania,bromided silica-titania, fluorided-chlorided silica-titania, sulfatedsilica-titania, fluorided silica-zirconia, chlorided silica-zirconia,bromided silica-zirconia, fluorided-chlorided silica-zirconia, sulfatedsilica-zirconia, fluorided silica-coated alumina, chloridedsilica-coated alumina, bromided silica-coated alumina,fluorided-chlorided silica-coated alumina, sulfated silica-coatedalumina, fluorided mullite, chlorided mullite, bromided mullite,fluorided-chlorided mullite, or sulfated mullite.

Aspect 37. A continuous process according to any one of Aspects 32-34,wherein the chemically-treated solid oxide comprises, consists of,consists essentially of, or is selected from fluorided silica-alumina,fluorided-chlorided silica-alumina, sulfated silica-alumina, fluoridedsilica-coated alumina, fluorided-chlorided silica-coated alumina, asulfated silica-coated alumina, fluorided mullite, fluorided-chloridedmullite, or sulfated mullite.

Aspect 38. A continuous process according to any one of Aspects 32-34,wherein the polyanionic solid comprises, consists essentially or,consists of, or is selected from a fluorided-chlorided silica-coatedalumina, a fluorided silica-coated alumina, or a chlorided silica-coatedalumina.

Aspect 39. A continuous process according to any one of Aspects 32-24,wherein the solid oxide comprises, consists of, consists essentially of,or is selected from alumina, silica, silica-alumina, silica-coatedalumina, silica-titania, silica-zirconia, mullite, or any combinationthereof.

Aspect 40. A continuous process according to any one of Aspects 32-39,wherein the silica-coated alumina comprises from about 10 to about 80wt. % silica, based on the weight of the silica-coated alumina; thefluorided-chlorided silica-coated alumina comprises from about 2 toabout 15 wt. % F, based on the weight of the fluorided-chloridedsilica-coated alumina; and/or the fluorided-chlorided silica-coatedalumina comprises from about 1 to about 10 wt. % Cl, based on the weightof the fluorided-chlorided silica-coated alumina.

Aspect 41. A continuous process according to any one of Aspects 36-38and 40, wherein the fluorided-chlorided silica-coated alumina isproduced by a process comprising: (a) calcining a silica-coated aluminaat a peak calcining temperature to produce a calcined silica-coatedalumina; (b) contacting the calcined silica-coated alumina with achlorine-containing compound and calcining at a peak chloridingtemperature to produce a chlorided silica-coated alumina; and (c)contacting the chlorided silica-coated alumina with afluorine-containing compound and calcining at a peak fluoridingtemperature to produce the fluorided-chlorided silica-coated alumina.

Aspect 42. A continuous process according to any one of Aspects 34-41,wherein the fluorided-chlorided silica-coated alumina has: a pore volumein a range from about 0.9 to about 2.0 mL/g; and a surface area in arange from about 200 to about 700 m²/g.

Aspect 43. A continuous process according to any one of Aspects 1-13,wherein the polyanionic solid comprises, consists of, consistsessentially of, or is selected from an organic base moiety immobilizedon a solid support.

Aspect 44. A continuous process according to Aspect 43, wherein theorganic base moiety immobilized on a solid support comprises structuralunits having the general formula (I):

SS-[A]_(x)-L-B  (I);

wherein SS is a solid support, A is an anchor moiety, L is a direct bondor linking moiety, and B is an organic base moiety, and wherein x is 0to 3.

Aspect 45. A continuous process according to Aspect 44, wherein theorganic base moiety B has the general formula:

[—CR¹R²—O]⁻, [—CR¹R²—S]⁻, [—CR¹R²—NR³]⁻, or [—CR¹R²—PR³]⁻,

wherein each of R¹ and R², independently or together, are selected fromH or an unbranched or branched, acyclic or cyclic, C₁-C₁₂ hydrocarbylresidue; and R³ is selected independently from hydrogen or a substitutedor an unsubstituted C₁-C₁₂ hydrocarbyl.

Aspect 46. A continuous process according to Aspect 45, wherein each ofR¹ and R², independently or together, are selected from H, methyl,ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, tert-butyl, 1-(2-methyl)propyl, 2-(2-methyl)propyl, 1-pentyl, 1-(2-methyl)pentyl, 1-hexyl,1-(2-ethyl)hexyl, 1-heptyl, 1-(2-propyl)heptyl, 1-octyl, 1-nonyl,1-decyl, 1-undecyl, 1-dodecyl, adamantyl, cyclopentyl,methylcyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl,cyclooctyl, norbornyl, phenyl, napthyl, tolyl, or xylyl.

Aspect 47. A continuous process according to Aspect 44, wherein theorganic base moiety B of the general formula SS-[A]_(x)-L-B (I) has theformula:

wherein Y is selected from a halide or a C₁-C₆ hydrocarbyl, and m is0-4; and

wherein

is the SS-[A]_(x)-L portion of formula (I).

According to this Aspect, the organic base moiety immobilized on a solidsupport has the following structure, as defined in these Aspects:

Aspect 48. A continuous process according to Aspect 44, wherein theorganic base moiety B of the general formula SS-[A]_(x)-L-B (I) has theformula:

wherein Y is selected from a halide or a C₁-C₆ hydrocarbyl, m is 0-4,and R⁶ is selected from a C₁-C₆ alkyl or aryl; and

wherein

is the SS-[A]_(x)-L portion of formula (I).

According to this Aspect, the organic base moiety immobilized on a solidsupport has the following structure, as defined in these Aspects:

Aspect 49. A continuous process according to Aspect 43, wherein theorganic base moiety immobilized on a solid support has the generalformula (II):

SS-[O]_(3-n)—Si(OR⁴)_(n)—B  (II);

wherein n is 0, 1, or 2, and each R⁴ is selected independently from asubstituted or an unsubstituted C₁-C₁₂ hydrocarbyl.

Aspect 50. A continuous process according to Aspect 43, wherein theorganic base moiety immobilized on a solid support comprises structuralunits having the general formula (I):

SS-[A]_(x)-L-B  (I);

wherein the organic base moiety B is selected from [—CR¹R²—O]⁻,[—CR¹R²—S]⁻, [—CR¹R²—NR³]⁻, or [—CR¹R²—PR³]⁻, wherein each of R¹ and R²,independently or together, are selected from H or an unbranched orbranched, acyclic or cyclic, C₁-C₁₂ hydrocarbyl residue; and R³ isselected independently from hydrogen or a substituted or anunsubstituted C₁-C₁₂ hydrocarbyl; and

A is selected from [—YR⁵R⁶—CH²], wherein

-   -   a) Y is N⁺ or C, and R⁵ and R⁶ are selected independently from        hydrogen, or a substituted or an unsubstituted C₁-C₁₂        hydrocarbyl, or    -   b) Y is Si, and R⁵ and R⁶ are selected independently from a        substituted or an unsubstituted C₁-C₁₂ hydrocarbyl, or a        substituted or an unsubstituted C₁-C₁₂ hydrocarbyloxide.

Aspect 51. A continuous process according to any one of the precedingAspects, wherein the diluent comprises carbon dioxide.

Aspect 52. A continuous process according to any one of the precedingAspects, wherein at least a portion of the diluent comprises theα,β-unsaturated carboxylic acid or the salt thereof, formed in theprocess.

Aspect 53. A continuous process according to any one of Aspects 1-50,wherein the diluent comprises any suitable non-protic solvent, or anynon-protic solvent disclosed herein.

Aspect 54. A continuous process according to any one of Aspects 1-50,wherein the diluent comprises any suitable non-protic solvent or anynon-protic solvent disclosed herein, and carbon dioxide (CO₂) underpressure.

Aspect 55. A continuous process according to any one of Aspects 1-50,wherein the diluent comprises any suitable non-protic solvent or anynon-protic solvent disclosed herein, and the olefin and carbon dioxide(CO₂) under pressure.

Aspect 56. A continuous process according to any one of Aspects 1-50,wherein the diluent comprises carbon dioxide (CO₂) under pressure.

Aspect 57. A continuous process according to any one of Aspects 1-50,wherein the diluent comprises the olefin and carbon dioxide (CO₂) underpressure.

Aspect 58. A continuous process according to any one of Aspects 1-50,wherein the diluent comprises the ethylene and carbon dioxide (CO₂)under pressure.

Aspect 59. A continuous process according to any one of Aspects 1-50,wherein the diluent comprises any suitable weakly coordinating ornon-coordinating solvent, or any weakly coordinating or non-coordinatingsolvent disclosed herein.

Aspect 60. A continuous process according to any one of Aspects 1-50,wherein the diluent comprises any suitable aromatic hydrocarbon solvent,or any aromatic hydrocarbon solvent disclosed herein, e.g., benzene,xylene, toluene, etc.

Aspect 61. A continuous process according to any one of Aspects 1-50,wherein the diluent comprises any suitable ether solvent, or any ethersolvent disclosed herein, e.g., THF, dimethyl ether, diethyl ether,dibutyl ether, etc.

Aspect 62. A continuous process according to any one of Aspects 1-50,wherein the diluent comprises any suitable carbonyl-containing solvent,or any carbonyl-containing solvent disclosed herein, e.g., ketones,esters, amides, etc. (e.g., acetone, ethyl acetate,N,N-dimethylformamide, etc.).

Aspect 63. A continuous process according to any one of Aspects 1-50,wherein the diluent comprises any suitable halogenated aromatichydrocarbon solvent, or any halogenated aromatic hydrocarbon solventdisclosed herein, e.g., chlorobenzene, dichlorobenzene, etc.

Aspect 64. A continuous process according to any one of Aspects 1-50,wherein the diluent comprises THF, 2,5-Me₂THF, methanol, acetone,toluene, chlorobenzene, pyridine, or a combination thereof.

Aspect 65. A continuous process according to any one of Aspects 1-64,wherein the contacting step in the third stage further comprisescontacting an additive selected from an acid, a base, or a reductant.

Aspect 66. A continuous process according to any one of Aspects 1-2 or5-64, wherein the contacting step of the first stage further comprisescontacting the transition metal precursor compound comprising at leastone first ligand with the at least one second ligand.

Aspect 67. A continuous process according to any one of Aspects 1-2 or5-64, wherein the contacting step of the first stage comprisescontacting (a) the transition metal precursor compound with (b) the atleast one second ligand to form a pre-contacted mixture, followed bycontacting the pre-contacted mixture with (c) the olefin, (d) carbondioxide (CO₂), and (e) the diluent to form the first composition.

Aspect 68. A continuous process according to any one of Aspects 1-2 or5-64, wherein the contacting step of the first stage comprisescontacting the components (a)-(e) in any order.

Aspect 69. A continuous process according to any one of Aspects 1-64wherein the contacting step of the second stage comprises contacting thepolyanionic solid with a second diluent to form a mixture, followed bycontacting the mixture with the first composition to form the secondcomposition.

Aspect 70. A continuous process according to any one of Aspects 1-64,wherein the contacting step of the third stage further comprisescontacting the second composition with any suitable acid, or any aciddisclosed herein, e.g., HCl, acetic acid, etc.

Aspect 71. A continuous process according to any one of Aspects 1-64,wherein the contacting step of the third stage further comprisescontacting the second composition with any suitable solvent, or anysolvent disclosed herein, e.g., carbonyl-containing solvents such asketones, esters, amides, etc. (e.g., acetone, ethyl acetate,N,N-dimethylformamide), alcohols, water, etc.

Aspect 72. A continuous process according to any one of the precedingAspects, wherein the contacting step of the third stage furthercomprises heating the second composition to any suitable temperature, ora temperature in any range disclosed herein, e.g., from 50 to 1000° C.,from 100 to 800° C., from 150 to 600° C., from 250 to 550° C., etc.

Aspect 73. A continuous process according to any one of the precedingAspects, wherein the molar yield of the α,β-unsaturated carboxylic acid,or the salt thereof, based on the metalalactone (in those precedingAspects comprising a metalalactone) or based on the transition metalprecursor compound (in those preceding Aspects comprising a transitionmetal precursor compound) is in any range disclosed herein, e.g., atleast 20%, at least 40%, at least 60%, at least 80%, at least 100%, atleast 120%, at least 140%, at least 160%, at least 180%, at least 200%,at least 250%, at least 300%, at least 350%, at least 400%, at least450%, or at least 500%, etc.

Aspect 74. A continuous process according to any one of the precedingAspects, wherein the contacting step in any one or more of the firststage, the second stage, and/or the third stage is conducted at anysuitable pressure or at any pressure disclosed herein, e.g., from 5 psig(34 KPa) to 10,000 psig (68,948 KPa), from 45 psig (310 KPa) to 1000psig (6,895 KPa), etc.

Aspect 75. A continuous process according to any one of the precedingAspects, wherein the contacting step in any one or more of the firststage, the second stage, and/or the third stage conducted at anysuitable temperature or at any temperature disclosed herein, e.g., from0° C. to 250° C., from 0° C. to 95° C., from 15° C. to 70° C., etc.

Aspect 76. A continuous process according to any one of the precedingAspects, wherein the contacting step in any one or more of the secondstage and/or the third stage is conducted at any suitable weight hourlyspace velocity (WHSV) or any WHSV disclosed herein, e.g., from 0.05 to50 hr⁻¹, from 1 to 25 hr⁻¹, from 1 to 5 hr⁻¹, etc., based on the amountof the polyanionic solid.

Aspect 77. A continuous process according to any one of the precedingAspects, wherein the process further comprises a step of isolating theα,β-unsaturated carboxylic acid, or the salt thereof, e.g., using anysuitable separation/purification procedure or anyseparation/purification procedure disclosed herein, e.g., evaporation,distillation, chromatography, etc.

Aspect 78. A continuous process according to any one of Aspects 1-77,wherein the polyanionic solid of the contacting step (2) comprises afixed bed.

Aspect 79. A continuous process according to any one of Aspects 1-77,wherein the polyanionic solid of the contacting step (2) is eitherformed onto beads or is supported on an inorganic or organic carriermaterial.

Aspect 80. A continuous process according to any one of Aspects 1-79,wherein the α,β-unsaturated carboxylic acid or a salt thereof comprisesany suitable α,β-unsaturated carboxylic acid, or any α,β-unsaturatedcarboxylic acid disclosed herein, or a salt thereof, e.g., acrylic acid,methacrylic acid, 2-ethylacrylic acid, cinnamic acid, sodium acrylate,potassium acrylate, magnesium acrylate, sodium (meth)acrylate, etc.

Aspect 81. A continuous process according to any one of Aspects 1-2 or5-80, further comprising a step of contacting a transition metalprecursor compound comprising at least one first ligand, at least onesecond ligand, an olefin, and carbon dioxide (CO₂) to form themetalalactone compound.

Aspect 82. A continuous process according to any one of Aspects 3-81,wherein the metalalactone compound comprises the at least one secondligand.

Aspect 83. A continuous process according to any one of Aspects 1-2 or5-81, wherein the olefin comprises any suitable olefin or any olefindisclosed herein, e.g. ethylene, propylene, butene (e.g., 1-butene),pentene, hexene (e.g., 1-hexene), heptane, octene (e.g., 1-octene),styrene, etc.

Aspect 84. A continuous process according to any one of Aspects 1-2 or5-81, wherein the olefin is ethylene, and the step of contacting atransition metal precursor compound with an olefin and carbon dioxide(CO₂) is conducted using any suitable pressure of ethylene, or anypressure of ethylene disclosed herein, e.g., from 10 psig (69 KPa) to1,000 psig (6895 KPa), from 25 psig (172 KPa) to 500 psig (3,447 KPa),or from 50 psig (345 KPa) to 300 psig (2,068 KPa), etc.

Aspect 85. A continuous process according to any one of Aspects 1-2 or5-81, wherein the olefin is ethylene, and the step of contacting atransition metal precursor compound with an olefin and carbon dioxide(CO₂) is conducted using a constant addition of the olefin and carbondioxide to provide the second composition.

Aspect 86. A continuous process according to Aspect 85, wherein theethylene and carbon dioxide (CO₂) are constantly added in anethylene:CO₂ molar ratio of from 3:1 to 1:3.

Aspect 87. A continuous process according to any one of Aspects 1-2 or5-81, wherein the step of contacting a transition metal precursorcompound with the olefin and carbon dioxide (CO₂) is conducted using anysuitable pressure of CO₂, or any pressure of CO₂ disclosed herein, e.g.,from 20 psig (138 KPa) to 2,000 psig (13,790 KPa), from 50 psig (345KPa) to 750 psig (5,171 KPa), or from 100 psig (689 KPa) to 300 psig(2,068 KPa), etc.

Aspect 88. A continuous process according to any one of the precedingAspects, further comprising a step of monitoring the concentration of atleast one second composition, at least one elimination reaction product,or a combination thereof.

Aspect 89. A continuous process according to any one of Aspects 1-88,wherein the metal of the metalalactone or the metal of the transitionmetal precursor compound is a Group 6 or 8-11 transition metal.

Aspect 90. A continuous process according to any one of Aspects 1-88,wherein the metal of the metalalactone or the metal of the transitionmetal precursor compound is Cr, Mo, W, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag,Ir, Pt, or Au.

Aspect 91. A continuous process according to any one of Aspects 1-88,wherein the metal of the metalalactone or the metal of the transitionmetal precursor compound is Ni, Fe, or Rh.

Aspect 92. A continuous process according to any one of Aspects 1-88,wherein the metal of the metalalactone or the metal of the transitionmetal precursor compound is Ni.

Aspect 93. A continuous process according to any one of Aspects 1-88,wherein the metalalactone is a nickelalactone, e.g., any suitablenickelalactone or any nickelalactone disclosed herein.

Aspect 94. A continuous process according to any one of Aspects 1-93,wherein any of the first ligand, or the second ligand is any suitableneutral electron donor group and/or Lewis base, or any neutral electrondonor group and/or Lewis base disclosed herein.

Aspect 95. A continuous process according to any one of Aspects 1-93,wherein any of the first ligand, or the second ligand is a bidentateligand.

Aspect 96. A continuous process according to any one of Aspects 1-93,wherein any of the first ligand, or the second ligand comprises anolefin ligand or a diene ligand.

Aspect 97. A continuous process according to any one of Aspects 1-93,wherein any of the first ligand, or the second ligand comprises at leastone of a nitrogen, phosphorus, sulfur, or oxygen heteroatom.

Aspect 98. A continuous process according to any one of Aspects 1-93,wherein any of the first ligand, or the second ligand comprises or isselected from a diphosphine ligand, a diamine ligand, a diene ligand, adiether ligand, or dithioether ligand.

Aspect 99. A continuous process according to any one of Aspects 1-93,wherein the first ligand is a diene ligand and the second ligand is adiphosphine ligand.

Aspect 100. A continuous process according to any one of Aspects 1-99,further comprising a step of washing the regenerated polyanionic solidwith a solvent or the diluent following the third stage.

Aspect 101. A continuous process according to any one of Aspects 1-100,wherein the metal-containing base comprises any suitable base, or anybase disclosed herein, e.g., carbonates (e.g., Na₂CO₃, Cs₂CO₃, MgCO₃),hydroxides (e.g., Mg(OH)₂, NaOH), alkoxides (e.g., Al(O^(i)Pr)₃,Na(O^(t)Bu), Mg(OEt)₂), halides (e.g. NaCl, KCl, LiI) and the like.

Aspect 102. A continuous process according to any one of Aspects 1-101,wherein the step of contacting the reacted solid with themetal-containing base is carried out in the absence of an alkoxide, anaryloxide, an amide, an alkylamide, an arylamide, an amine, a hydride, aphosphazene, and/or substituted analogs thereof.

Aspect 103. A continuous process according to any one of Aspects 1-101,wherein the step of contacting the reacted solid with themetal-containing base is carried out in the absence of an alkoxide, anaryloxide, a hydride, and/or a phosphazene.

Aspect 104. A continuous process according to any one of Aspects 1-101,wherein the step of contacting the reacted solid with themetal-containing base is carried out in the absence of an aryloxide or ametal hydride.

Aspect 105. A continuous process according to any one of Aspects 1-101,wherein the step of contacting the reacted solid with themetal-containing base is carried out in the absence of anon-nucleophilic base.

Aspect 106. A continuous process according to any one of Aspects 1-105,wherein the polyanionic solid is unsupported.

Aspect 107. A continuous process according to any one of Aspects 1-105,wherein the polyanionic solid is supported.

Aspect 108. A continuous process according to any one of the precedingAspects, wherein the metalalactone compound, any ligand of themetalalactone compound, transition metal precursor compound, firstligand, second ligand, polyanionic solid, or metal cation is anysuitable metalalactone compound, ligand of the metalalactone compound,transition metal precursor compound, first ligand, second ligand,polyanionic solid, or metal cation or is any metalalactone compound,ligand of the metalalactone compound, transition metal precursorcompound, first ligand, second ligand, polyanionic solid, or metalcation disclosed herein.

Aspect 109. A continuous process for producing an α,β-unsaturatedcarboxylic acid or salt thereof, the process comprising:

-   -   1) in a first stage, contacting (a) a Group 8-10 transition        metal precursor compound comprising at least one first        ligand, (b) optionally, at least one second ligand, (c) an        olefin, (d) carbon dioxide (CO₂), and (e) a diluent to form a        first composition comprising a metalalactone compound; and    -   2) in a second stage, contacting an anionic polyaromatic resin        comprising associated metal cations with the first composition        to form a second composition comprising an adduct of the        metalalactone compound and the anionic polyaromatic resin; and    -   3) in a third stage, (a) contacting the second composition with        water to release a metal salt of an α,β-unsaturated carboxylic        acid and form a reacted polyaromatic resin; and (b) contacting        the reacted polyaromatic resin with a metal-containing base to        produce a regenerated polyanionic solid.

Aspect 110. A continuous process according to Aspect 109, wherein theanionic polyaromatic resin comprises an alkali metal or an alkalineearth metal oxide, hydroxide, alkoxide, aryloxide, amide, alkyl amide,arylamide, or carbonate.

Aspect 111. A continuous process according to any one of Aspects109-110, wherein the contacting step is carried out in the absence of anon-nucleophilic base.

We claim:
 1. A continuous process for producing an α,β-unsaturatedcarboxylic acid or salt thereof, the process comprising (a) in a firststage, contacting (i) a Group 6 or a Group 8-11 transition metalprecursor compound comprising at least one first ligand, (ii)optionally, at least one second ligand, (iii) an olefin, (iv) carbondioxide (CO₂), and (v) a diluent to form a first composition; (b) in asecond stage, contacting a polyanionic solid with associated cationswith the first composition to form a second composition, wherein (i) thepolyanionic solid with associated cations comprises a chemically-treatedsolid oxide comprising at least one solid oxide that has been treatedwith at least one electron withdrawing anion, (ii) the at least onesolid oxide comprises silica, alumina, silica-alumina, silica-coatedalumina, mullite, or any combination thereof, and (iii) the at least oneelectron withdrawing anion comprises fluoride, chloride, phosphate,triflate, sulfate, bisulfate, fluorosulfate, or any combination thereof;and (c) in a third stage, (i) contacting the second composition with apolar solvent to release a metal salt of an α,β-unsaturated carboxylicacid and form a reacted solid; and (ii) contacting the reacted solidwith a metal-containing base to produce a regenerated polyanionic solidwith associated cations.
 2. A continuous process according to claim 1,wherein contacting the second composition with the polar solvent in thethird stage to form the reacted solid is carried out before contactingthe reacted solid with the metal-containing base.
 3. A continuousprocess according to claim 1, wherein contacting the second compositionwith the polar solvent in the third stage to form the reacted solid iscarried out at the same time as contacting the reacted solid with themetal-containing base.
 4. A continuous process according to claim 1,wherein: the at least one solid oxide comprises silica, alumina, orsilica-coated alumina; and the at least one electron withdrawing anioncomprises fluoride, sulfate, fluorosulfate, or any combination thereof.5. A continuous process according to claim 1, wherein: the at least onesolid oxide comprises alumina or silica-coated alumina; and the at leastone electron withdrawing anion comprises fluoride or sulfate.
 6. Acontinuous process according to claim 1, wherein the polar solventcomprises water, an aliphatic alcohol, an aromatic alcohol, an inorganicacid, an organic acid, or a combination thereof.
 7. A continuous processaccording to claim 1, wherein the polar solvent comprises water and themetal-containing base comprises an alkali metal alkoxide.
 8. Acontinuous process according to claim 1, further comprising the step of:(d) in the third stage or in a subsequent stage, washing the regeneratedpolyanionic solid with associated cations with water.
 9. A continuousprocess according to claim 1, wherein the chemically-treated solid oxidecomprises silica-coated alumina treated with at least oneelectron-withdrawing anion, and the silica-coated alumina has a weightratio of alumina to silica in a range from about 1:1 to about 100:1. 10.A continuous process according to claim 1, wherein thechemically-treated solid oxide comprises fluorided alumina, sulfatedalumina, fluorided silica-alumina, sulfated silica-alumina, fluoridedsilica-coated alumina, sulfated silica-coated alumina, fluoridedmullite, or sulfated mullite.
 11. A continuous process according toclaim 1, wherein the chemically-treated solid oxide comprises sulfatedalumina or fluorided silica-coated alumina.
 12. A continuous processaccording to claim 1, wherein the at least one solid oxide comprisessilica-coated alumina, and wherein the silica-coated alumina comprisesfrom about 10 wt. % to about 80 wt. % silica, based on the weight of thesilica-coated alumina.
 13. A continuous process according to claim 1,wherein: (a) the first stage and the second stage are carried out (i)concurrently in a first reactor and a second reactor, respectively, or(ii) sequentially in a single reactor; and/or (b) the first stage, thesecond stage, and the third stage are carried out simultaneously in afirst reactor, a second reactor, and a third reactor, respectively. 14.A continuous process according to claim 1, further comprising, in afourth stage, drying or partially drying the regenerated polyanionicsolid with associated cations.
 15. A continuous process according toclaim 14, wherein the second stage, the third stage, and the fourthstage are carried out: (a) concurrently in a second reactor, a thirdreactor, and a fourth reactor, respectively; or (b) sequentially in asingle reactor.
 16. A continuous process according to claim 1, whereinthe polyanionic solid with associated cations comprises associated metalcations selected from lithium, sodium, potassium, magnesium, calcium,strontium, barium, aluminum, or zinc.
 17. A continuous process accordingto claim 1, wherein the diluent comprises a non-protic solvent, carbondioxide (CO₂), and/or at the α,β-unsaturated carboxylic acid or the saltthereof, formed in the process.
 18. A continuous process according toclaim 1, wherein the metal of the transition metal precursor compound isCr, Mo, W, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, or Au, and whereinany of the first ligand, or the second ligand comprises at least one ofa nitrogen, phosphorus, sulfur, or oxygen heteroatom.
 19. A continuousprocess for producing an α,β-unsaturated carboxylic acid or saltthereof, the process comprising (a) in a first stage, obtaining orproviding a first composition comprising a metalalactone compound of aGroup 6 or a Group 8-11 transition metal and a diluent; (b) in a secondstage, contacting a polyanionic solid with associated cations with thefirst composition to form a second composition, wherein (i) thepolyanionic solid with associated cations comprises a chemically-treatedsolid oxide comprising at least one solid oxide that has been treatedwith at least one electron withdrawing anion, (ii) the at least onesolid oxide comprises silica, alumina, silica-alumina, silica-coatedalumina, mullite, or any combination thereof, and (iii) the at least oneelectron withdrawing anion comprises fluoride, chloride, phosphate,triflate, sulfate, bisulfate, fluorosulfate, or any combination thereof;and (c) in a third stage, (i) contacting the second composition with apolar solvent to release a metal salt of an α,β-unsaturated carboxylicacid and form a reacted solid; and (ii) contacting the reacted solidwith a metal-containing base to produce a regenerated polyanionic solidwith associated cations.
 20. A continuous process according to claim 19,wherein the second composition comprising an adduct of the metalalactonecompound and the polyanionic solid with associated cations.
 21. Acontinuous process according to claim 19, wherein contacting the secondcomposition with the polar solvent in the third stage to form thereacted solid is carried out (a) before contacting the reacted solidwith the metal-containing base, or (b) at the same time as contactingthe reacted solid with the metal-containing base.
 22. A continuousprocess according to claim 19, wherein the chemically-treated solidoxide comprises sulfated alumina or fluorided silica-coated alumina. 23.A continuous process according to claim 19, wherein the polar solventcomprises water, an aliphatic alcohol, an aromatic alcohol, an inorganicacid, an organic acid, or a combination thereof.
 24. A continuousprocess according to claim 19, further comprising the step of: (d) inthe third stage or in a subsequent stage, washing the regeneratedpolyanionic solid with associated cations with water.
 25. A continuousprocess according to claim 19, wherein the at least one solid oxidecomprises silica-coated alumina, and wherein the silica-coated aluminacomprises from about 10 wt. % to about 80 wt. % silica, based on theweight of the silica-coated alumina.
 26. A continuous process accordingto claim 19, wherein: (a) the first stage and the second stage arecarried out (i) concurrently in a first reactor and a second reactor,respectively, or (ii) sequentially in a single reactor; and/or (b) thefirst stage, the second stage, and the third stage are carried outsimultaneously in a first reactor, a second reactor, and a thirdreactor, respectively.
 27. A continuous process according to claim 19,further comprising, in a fourth stage, drying or partially drying theregenerated polyanionic solid with associated cations, wherein thesecond stage, the third stage, and the fourth stage are carried out: (a)concurrently in a second reactor, a third reactor, and a fourth reactor,respectively; or (b) sequentially in a single reactor.
 28. A continuousprocess according to claim 19, wherein the polyanionic solid withassociated cations comprises associated metal cations selected fromlithium, sodium, potassium, magnesium, calcium, strontium, barium,aluminum, or zinc.
 29. A continuous process according to claim 19,wherein the metal of the transition metal precursor compound is Cr, Mo,W, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, or Au, and wherein any of thefirst ligand, or the second ligand comprises at least one of a nitrogen,phosphorus, sulfur, or oxygen heteroatom.
 30. A continuous process forproducing an α,β-unsaturated carboxylic acid or salt thereof, theprocess comprising (a) in a first stage, contacting (i) Ni(COD)₂, (ii) adiphosphine ligand, (iii) ethylene, (iv) carbon dioxide (CO₂), and (v) adiluent to form a first composition; (b) in a second stage, contacting apolyanionic solid with associated cations with the first composition toform a second composition, wherein (i) the polyanionic solid withassociated cations comprises sulfated alumina or fluorided silica-coatedalumina with associated cations selected from lithium, sodium, orpotassium; and (c) in a third stage, (i) contacting the secondcomposition with a polar solvent to release a metal salt of acrylic acidand form a reacted solid; and (ii) contacting the reacted solid with alithium-, sodium-, or potassium-containing base to produce a regeneratedpolyanionic solid with associated cations.